EP2465892A1 - Silicon stabilisers for polyurethane or polyisocyanurate rigid foams - Google Patents
Silicon stabilisers for polyurethane or polyisocyanurate rigid foams Download PDFInfo
- Publication number
- EP2465892A1 EP2465892A1 EP11189690A EP11189690A EP2465892A1 EP 2465892 A1 EP2465892 A1 EP 2465892A1 EP 11189690 A EP11189690 A EP 11189690A EP 11189690 A EP11189690 A EP 11189690A EP 2465892 A1 EP2465892 A1 EP 2465892A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyether
- polyurethane
- foam
- foams
- polyisocyanurate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006260 foam Substances 0.000 title claims abstract description 109
- 239000011495 polyisocyanurate Substances 0.000 title claims abstract description 39
- 229920000582 polyisocyanurate Polymers 0.000 title claims abstract description 39
- 239000004814 polyurethane Substances 0.000 title claims abstract description 38
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 35
- 239000003381 stabilizer Substances 0.000 title claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title description 2
- 229910052710 silicon Inorganic materials 0.000 title 1
- 239000010703 silicon Substances 0.000 title 1
- 229920000570 polyether Polymers 0.000 claims abstract description 92
- 239000000203 mixture Substances 0.000 claims abstract description 76
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 74
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 229920005862 polyol Polymers 0.000 claims abstract description 22
- 150000003077 polyols Chemical class 0.000 claims abstract description 21
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 12
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003063 flame retardant Substances 0.000 claims abstract description 10
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- -1 siloxanes Chemical class 0.000 claims description 39
- 125000002947 alkylene group Chemical group 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 14
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 13
- 239000011496 polyurethane foam Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000011810 insulating material Substances 0.000 claims description 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- 230000001413 cellular effect Effects 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 31
- 239000004872 foam stabilizing agent Substances 0.000 description 20
- 238000009472 formulation Methods 0.000 description 20
- 230000007547 defect Effects 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 18
- 238000005187 foaming Methods 0.000 description 14
- 150000003254 radicals Chemical class 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002905 metal composite material Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000003380 propellant Substances 0.000 description 7
- 238000010276 construction Methods 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 5
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229920005669 high impact polystyrene Polymers 0.000 description 4
- 239000004797 high-impact polystyrene Substances 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 125000005011 alkyl ether group Chemical group 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 239000002666 chemical blowing agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- ATLPLEZDTSBZQG-UHFFFAOYSA-L dioxido-oxo-propan-2-yl-$l^{5}-phosphane Chemical compound CC(C)P([O-])([O-])=O ATLPLEZDTSBZQG-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000013038 hand mixing Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- ZUFQCVZBBNZMKD-UHFFFAOYSA-M potassium 2-ethylhexanoate Chemical compound [K+].CCCCC(CC)C([O-])=O ZUFQCVZBBNZMKD-UHFFFAOYSA-M 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000009751 slip forming Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- 125000006823 (C1-C6) acyl group Chemical group 0.000 description 1
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- YWDFOLFVOVCBIU-UHFFFAOYSA-N 1-dimethoxyphosphorylpropane Chemical compound CCCP(=O)(OC)OC YWDFOLFVOVCBIU-UHFFFAOYSA-N 0.000 description 1
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 description 1
- WMNWJTDAUWBXFJ-UHFFFAOYSA-N 3,3,4-trimethylheptane-2,2-diamine Chemical compound CCCC(C)C(C)(C)C(C)(N)N WMNWJTDAUWBXFJ-UHFFFAOYSA-N 0.000 description 1
- FZQMJOOSLXFQSU-UHFFFAOYSA-N 3-[3,5-bis[3-(dimethylamino)propyl]-1,3,5-triazinan-1-yl]-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCN1CN(CCCN(C)C)CN(CCCN(C)C)C1 FZQMJOOSLXFQSU-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001251094 Formica Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004614 Process Aid Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000012971 dimethylpiperazine Substances 0.000 description 1
- NVYQDQZEMGUESH-UHFFFAOYSA-N dimethylsilyloxy(dimethyl)silane Chemical compound C[SiH](C)O[SiH](C)C NVYQDQZEMGUESH-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- ILEDWLMCKZNDJK-UHFFFAOYSA-N esculetin Chemical compound C1=CC(=O)OC2=C1C=C(O)C(O)=C2 ILEDWLMCKZNDJK-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 235000019589 hardness Nutrition 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N iso-pentane Natural products CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 1
- COPLXRFZXQINJM-UHFFFAOYSA-N isocyanic acid;hydrate Chemical compound O.N=C=O COPLXRFZXQINJM-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000013518 molded foam Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
Definitions
- the invention relates to polyethersiloxanes and their use as foam stabilizers in the production of polyurethane or polyisocyanurate foams, in particular rigid foams, which offer particularly advantageous performance properties, such as low thermal conductivity and in particular a good surface quality.
- cell stabilizing additives are used, which should provide a fine-celled, uniform and low-interference foam structure and thus the performance characteristics, especially the thermal insulation capacity, of the rigid foam substantially positive influence.
- Particularly effective are surfactants based on polyether-modified siloxanes, which are therefore the preferred type of foam stabilizers.
- foam stabilizer Since there are a variety of different rigid foam formulations for different applications, which make individual demands on the foam stabilizer, polyether siloxanes of different structures are used. One of the selection criteria for the foam stabilizer is the propellant contained in the rigid foam formulation.
- the EP 0 570 174 B1 describes a polyether siloxane of the structure (CH 3 ) 3 SiO [SiO (CH 3 ) 2 ] x [SiO (CH 3) R] y Si (CH 3) 3, the radicals R consist of a condition attached to the siloxane via an SiC bond polyethylene oxide which is end-capped at the other chain end by a C 1 -C 6 acyl group.
- This foam stabilizer is suitable for the production of rigid polyurethane foams using organic blowing agents, in particular chlorofluorocarbons such as CFC-11.
- hydrochlorofluorohydrocarbons such as. HCFC-123.
- hydrochlorofluorohydrocarbons such as. HCFC-123.
- the radicals R consist here of SiC-bonded polyalkylene oxides which are composed of propylene oxide and ethylene oxide and can have a hydroxy, methoxy or acyloxy function at the chain end.
- the minimum proportion of ethylene oxide in the polyether is 25 percent by mass.
- the EP 0 877 045 B1 describes analogous structures for this preparation, which stand out from the first-mentioned foam stabilizers by a comparatively higher molecular weight and by the combination of two polyether substituents on the siloxane chain.
- polyether siloxanes in which the end group of polyethers is either a free OH group, an alkyl ether group (preferably methyl) or an ester is described as foam stabilizers. Particular preference is given to using those polyethersiloxanes which have free OH functions.
- the use of the special polyethersiloxanes in particular should have a positive influence on the fire behavior.
- organo-modified siloxanes are described for the preparation of polyurethane foams which, in addition to alkyl and polyether substituents, also carry side chains with tertiary OH groups. Thus, additional substituents are introduced here.
- the polyethers used here are usually methyl-end-capped. In general, the polyethers have no special arrangement of the alkylene oxide units, so that in the case of a non-endcapping there is no defined OH functionality.
- US 4,746,683 describes the improvement of the open-celledness of highly flexible flexible foams by the use of polyethersiloxanes, wherein the polyethers are present in a high proportion. or tert. Wear OH groups.
- the Siloxanes contain a maximum of 10 Si atoms and the polyethers consist of 3 to 13 oxyalkylene units.
- foam stabilizers described in these documents do not offer the desired optimum foaming properties in the full range of different rigid foam formulations, and improvements in foam stabilizers over the prior art are desirable in many applications in order to further optimize the performance properties of the rigid foams, in particular with regard to thermal conductivity and the foam defects on the surface.
- the foam defects on the surface are increasingly becoming the focus of attention.
- voids or bubbles lying directly under the cover layer may form in the foam on the topcoat surface in the form of dents or blisters and so on give the viewer a bad quality impression.
- the top layer adhesion and thermal insulation usually deteriorate in their initial values and can also be subject to increased aging with further deterioration of the values. This problem is also known in polyurethane or polyisocyanurate insulation boards.
- foam stabilizer Polyether siloxanes with so-called end-capped polyether side groups, ie polyethers, which instead of an OH group, a terminal alkyl ether or Ester group are known for relatively low-surface quality.
- foam stabilizers are less soluble in polyol formulations than OH-functional products.
- insoluble foam stabilizers in pre-formulated polyol systems which are customary in the market, especially for the areas of refrigerator insulation and metal composite elements, is precluded by the risk of phase separation of the formulation during longer storage times before processing.
- a preferred object of the invention was also the development of rigid polyurethane or polyisocyanurate foams and their underlying formulations, which have particularly advantageous performance characteristics such.
- An object of the present invention are therefore polyethersiloxanes of the formula (I), as described below and in the claims, which have scarcely primary but predominantly secondary or tertiary OH groups, and the use of the polyethersiloxanes according to the invention for the production of polyurethane foams and Polyisocyanuratschaumstoffen.
- a further subject matter of the present invention is a composition suitable for producing rigid polyurethane or polyisocyanurate foams comprising at least one isocyanate component, at least one polyol component, at least one foam stabilizer, at least one urethane and / or isocyanurate catalyst, water and / or blowing agent , and optionally at least one flame retardant and / or further additives, which is characterized in that at least one polyether siloxane according to the invention is contained as a foam stabilizer, a process for the preparation of rigid polyurethane or polyisocyanurate foams, by reacting this composition and the resulting polyurethane or polyisocyanurate foams.
- the present invention is the use of rigid polyurethane or polyisocyanurate foams of the invention as insulation boards, insulation and in the form of metal composite elements as Construction element for the construction of buildings, cold rooms, refrigerated containers and trucks and a cooling apparatus, which has a polyurethane or polyisocyanurate rigid foam according to the invention as an insulating material.
- the polyethersiloxanes of the invention have the advantage that polyurethane or PolyisocyanuratShume, in particular rigid foams can be produced with you, which are characterized by good fineness and good insulating properties and at the same time have little foam defects.
- foam defects voids, densities
- the foam defects problematic in composite systems made of rigid foam with flexible or rigid cover layers at the interface with the cover layer can be effectively minimized with the aid of the polyether siloxanes according to the invention over the prior art.
- R 1 and R 2 are the same or different
- R 1 and / or R 2 are methyl or R
- R is the same or different - (CH 2 ) x -O- (CH 2 -CR'R "-O) y -R ''', R ', R ", equal or different, are -H, -CH 3 , -CH 2 CH 3 , or phenyl radical
- R '" -H, -alkyl or -acyl radical, preferably -alkyl radical having 1 to 40, preferably 1 to 24, carbon atoms or -acyl radical having 1 to 40, preferably 1 to 24, carbon atoms, wherein the
- polyether siloxanes of the formula (I) according to the invention are copolymers which are usually polydisperse compounds as a result of the preparation, so that with regard to the parameters n, m, x and y only average values can be stated.
- the ratio of primary to secondary / tertiary OH groups may, for. B. be influenced by the polyether used in the preparation or by the amount of the capping reagent used.
- the ratio of primary to secondary and tertiary OH end groups can be determined by NMR methods. Preferably, the determination is carried out as described below with a NMR spectrometer with computer unit and autosampler with 5 mm probe head from Bruker, type 400 MHz, 10 mm QNP using 5 mm plastic test tubes and caps, both from Norell Inc. The Sampling takes place using Pasteur pipettes from Brand.
- Reagents used are: Deuterochloroform (CDCl 3 ) from Deutro, degree of deuteration 99.8%), molecular sieve A3 from Merck (for removal of water residues from the solvent).
- the specified amount of sample is introduced into a clean NMR tube and mixed with the indicated volume of CDCl 3 .
- the sample tube is closed with the plastic cap and the sample is homogenized by shaking. After all air bubbles have settled on the surface, the sample is measured in the NMR spectrometer.
- the assignment of the individual signals is familiar to the person skilled in the art or, if appropriate, can be carried out by comparison with the signals of suitable example substances.
- a suitable accelerator can be determined by the person skilled in the art by measuring model substances in which the molar ratio is known. Suitable accelerators are those in which the measured ratio deviates from the actual ratio by a maximum of 5%. For example, chromium acetylacetonate which is added in concentrations of about 0.8% by mass, based on the amount of sample, can be used as the accelerator.
- polyether substituents are in the comb position (lateral) of the siloxane chain (m is not equal to 0).
- the alkylene oxide units denoted by the index y are preferably ethylene oxide, propylene oxide, n-butylene oxide, isobutylene oxide and styrene oxide.
- the mole fraction of ethylene oxide is preferably at least 45 mol%, more preferably at least 65 mol%.
- the sequence of the various alkylene oxide building blocks may be arbitrary, other than the endblock in OH-functional polyethers, i. it can either be statistical or subject to targeted block building.
- OH-functional polyether radicals a di-block structure consisting of a pure ethylene oxide block and the terminal end block of an alkylene oxide other than ethylene oxide may be particularly advantageous.
- the polyethers in a molecule may be the same or different from each other as long as the polyether mixture satisfies the above definitions. Furthermore, mixtures of different polyether siloxanes are also included, provided that either the mean values of the mixture in the o. Areas fall or corresponds to a component of the above definition.
- Particularly preferred polyether siloxanes according to the invention are those in which on average n + m + 2 is equal to 15 to 100, x is 3 and y is 5 to 25 and R 1 and R 2 are polyether radicals of the R type.
- polyethersiloxanes according to the present invention can in principle be obtained according to the processes known from the prior art for the preparation of polyethersiloxanes.
- the synthesis of the polyether siloxanes according to the invention is preferably carried out by a platinum-catalyzed reaction of Si-H-functional siloxanes with terminally unsaturated polyethers.
- a detailed description can be found in EP 1 520 870 , which is hereby incorporated by reference and belongs to the disclosure of the present invention.
- EP 0 493 836 shows the preparation of polyether-modified siloxanes used in flexible foams. Further examples for the preparation of corresponding siloxanes are, for example, in US 4,147,847 and US 4,855,379 described.
- the terminally unsaturated polyethers can be prepared by reacting terminally unsaturated starting alcohols, such as preferably allyl alcohol, be obtained with a variety of alkylene oxides, preferably under alkaline catalysis with, for example, alkali metal hydroxides or double metal cyanide catalysis (DMC catalysis).
- the sequence of the polyethers obtained is controlled via the metered addition of the alkylene oxides.
- Block structures can be obtained by first alkylene oxide A is added to the starting alcohol and after reaching a complete conversion, the alkylene oxide B is added and added.
- Statistical sequences can be obtained by using the alkylene oxides A and B in a mixture.
- the polyethers may optionally be subjected either directly to an aqueous work-up to give products with terminal OH function, or optionally to a further reaction step for end-capping, for example by reaction with methyl chloride to form a methyl ether. End group to Williamson. So is for example in EP 1 360 223 and the documents cited therein describe the preparation of olefinic polyethers with and without derivatization of the OH functionality.
- z. B. is that in the preparation of the polyether finally a block of on average from 0.5 to 5, preferably 1 to 3 alkylene oxide block per polyether molecule with R 'and / or R' 'is added not equal to -H.
- Suitable alkylene oxides for this end block are, for example, propylene oxide, butylene oxide, isobutylene oxide and styrene oxide.
- alkylene oxides can be used to prepare the polyether residues.
- the mole fraction of ethylene oxide should preferably be at least 45 mol%, more preferably at least 65%.
- the sequence of the various alkylene oxide building blocks can be chosen arbitrarily, apart from the endblock in the case of OH-functional polyethers, ie they can be obtained either by random incorporation or obtained by a targeted block construction.
- the polyethersiloxanes according to the invention can be used in all known applications in which polyethersiloxanes are used.
- the polyethersiloxanes according to the invention are preferably used for the production of polyurethane foams, polyisocyanurate foams, in particular for the production of rigid polyurethane or polyisocyanurate foams.
- the mass fraction of polyethersiloxane according to the invention is preferably from 0.1 to 10 pphp, preferably 0.5 to 5 pphp and particularly preferably 1 to 3 pphp.
- the composition according to the invention may comprise all isocyanate compounds suitable for the preparation of rigid polyurethane or polyisocyanurate foams.
- the composition according to the invention comprises one or more organic isocyanates having two or more isocyanate functions, such as 4,4'-diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI) and isophorone diisocyanate (IPDI).
- MDI 4,4'-diphenylmethane diisocyanate
- TDI toluene diisocyanate
- HMDI hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- polymeric MDI "crude MDI”
- condensed analogues having an average functionality of 2 to 4
- isomers of TDI in pure form or as a mixture of isomers.
- Suitable polyols for the purposes of this invention may be all organic substances having a plurality of isocyanate-reactive groups, as well as their preparations.
- Preferred polyols are all polyether polyols and polyester polyols commonly used to make polyurethane foams.
- polyether polyols can be obtained by reaction of polyhydric alcohols or amines with alkylene oxides.
- Polyester polyols are based on esters of polybasic carboxylic acids (which may be either aliphatic, for example adipic acid or aromatic, for example phthalic acid or terephthalic acid) with polyhydric alcohols (usually glycols).
- a suitable ratio of isocyanate and polyol, expressed as the index of the formulation, i. the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g., OH groups, NH groups) multiplied by 100 is in the range of 10 to 1,000, preferably 80 to 350.
- the composition according to the invention preferably comprises one or more catalysts for the reactions isocyanate-polyol and / or isocyanate-water and / or the di- or trimerization of the isocyanate.
- Typical examples are the amines triethylamine, dimethylcyclohexylamine, tetramethylethylenediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenediamine, dimethylpiperazine, 1,2-dimethylimidazole, N-ethylmorpholine, tris (dimethylaminopropyl) hexahydro-1,3,5-triazine, dimethylaminoethanol, dimethylaminoethoxyethanol and bis (Dimethylaminoethyl) ether, tin compounds such as dibutyltin dilaurate or tin II-2-ethylhexanoate and potassium salts such as potassium acetate and potassium 2-ethylhexanoate.
- tin compounds such as dibutyltin dilaurate or tin II-2-ethylhexanoate and
- Suitable water contents in the context of this invention depend on whether one or more propellants are used in addition to the water or not. In the case of pure water-driven foams, the values are typically from 1 to 20 pphp, if other blowing agents are additionally used, the amount of use is reduced to usually 0 to 5 pphp.
- the composition comprises physical blowing agents.
- Suitable physical blowing agents for the purposes of this invention are gases, for example liquefied CO 2 , and volatile liquids, for example hydrocarbons having 3 to 5 carbon atoms, preferably cyclo, iso and n-pentane, hydrofluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, chlorofluorocarbons, preferably HCFC 141b, oxygen-containing compounds such as methyl formate and dimethoxymethane, or chlorohydrocarbons, preferably 1,2-dichloroethane.
- the composition according to the invention may comprise all known flame retardants which are suitable for the production of rigid polyurethane or polyisocyanurate foams.
- Suitable flame retardants in the context of this invention are preferably liquid organic phosphorus compounds, such as halogen-free organic phosphates, eg triethyl phosphate (TEP), halogenated phosphates, eg tris (1-chloro-2-propyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP) and organic Phosphonates, for example dimethylmethanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), or solids such as ammonium polyphosphate (APP) and red phosphorus.
- halogenated compounds for example halogenated polyols, and solids, such as expandable graphite and melamine, are suitable as flame retardants.
- Polyurethane or polyisocyanurate rigid foams can be produced with the composition according to the invention or with the method according to the invention.
- a preferred composition, in particular a polyurethane or polyisocyanurate rigid foam formulation in the context of this invention would give polyurethane or polyisocyanurate rigid foams with a density of 5 to 200 kg / m 3 , preferably from 5 to 50 kg / m 3 and would have the following composition: ⁇ u> Table 1: Typical foam formulation ⁇ / u> component weight proportion polyol 100 Amine Catalyst 0.05 to 5 Potassium trimerization 0 to 10 Polyethersiloxane of the formula (I) 0.5 to 5 water 0 to 20 propellant 0 to 40 Flame retardants 0 to 50 Isocyanate Index: 80 to 350
- the composition according to the invention is divided into two components before being reacted, the components must be mixed with one another in order to react them.
- This can be done by all methods familiar to the person skilled in the art, for example by hand mixing or preferably by means of low or high pressure foaming machines.
- discontinuous processes for example for the production of molded foams, refrigerators and panels, or continuous processes, for example in insulation boards and metal composite elements (in the so-called double-belt process), in blocks or in spray processes can be used.
- a special case is the 1- and 1.5-component can foams.
- the composition according to the invention is already reacted when filled into an aerosol can, which consists of the polyol, as well as all other isocyanate-reactive components, and the excess isocyanate forms a prepolymer.
- this prepolymer is discharged from the aerosol can as a foam with the aid of a propellant gas and cures by post-crosslinking under the influence of (air) moisture.
- the polyether siloxanes according to the invention can be used as foam stabilizers.
- the polyurethane or polyisocyanurate rigid foams according to the invention are obtainable.
- the rigid polyurethane or polyisocyanurate foams according to the invention preferably contain 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass and more preferably 1 to 3 parts by mass, based on 100 parts by mass of polyol component of the polyethersiloxanes according to the invention in bound and / or unbound form.
- the rigid polyurethane or polyisocyanurate foams according to the invention can be used as or for the production of insulating boards and insulating or insulating materials. In this way, cooling equipment, such. As refrigerators or freezers, accessible, which are characterized in that they have as insulating a polyurethane or polyisocyanurate rigid foam according to the invention.
- the compositions of the invention are used as PUR formulations (index less than 200), which are used in the foaming in a batch process in a mold. Often, these shapes are dimensioned so that the foaming mixture has long flow paths, thereby increasing the susceptibility to foam disturbances.
- susceptibility to foam disorders can be minimized.
- compositions according to the invention are preferably used in the production of refrigerators or other refrigeration units.
- the foaming mixture is injected into the wall of the so-called cabinet (and separately the door) and there must fill the available space between the outer cover layer and the inner cover layer (inliner).
- the foam is subjected to flow stress, which increases the risk of error formation.
- the materials used play an important role.
- the inliner is usually made of plastic and the outer shell of the refrigerator made of a metal top layer. There must be no foam defects resulting from the interaction with these materials or any contamination thereon.
- the compositions of the present invention show a superior ability to suppress foaming defects under these conditions. This gives even with the use of thin cover layers, such.
- the plastic cover layers can, for. As polypropylene, polyethylene or (high impact polystyrene) HIPS cover layers.
- the compositions according to the invention are used in the production of composite elements.
- the composition to be foamed (PUR and PIR formulations are used) is injected between two cover layers.
- Suitable cover layers are various materials. Usually it is metal cover layers for the production of metal composite elements, which are then in the Construction industry find use. But it can also be used on one or both sides of plastic topcoats.
- the resulting composite elements often called panels, can be used in various areas such as the construction industry (facades), in the automotive sector (caravan area), the fair construction (lightweight walls) or furniture manufacturing. Particularly in the case of two-sided use of plastic cover layers, very lightweight composite elements can be produced in this case.
- the following materials can be used as cover layers: PMMA (polymethyl methacrylate), HIPS (high impact polystyrene), PP (polypropylene), formica, fiber-reinforced paper types.
- PMMA polymethyl methacrylate
- HIPS high impact polystyrene
- PP polypropylene
- formica fiber-reinforced paper types.
- Particular problems here can arise from coatings on the metal cover layers or process aids (release agents) on plastic surfaces, which may be disadvantageous for the formation of the foam.
- the compositions according to the invention show advantages in terms of surface qualities, since there are fewer foam defects than when using siloxanes according to the prior art.
- the adhesion of the cover layers to the foam can also be improved.
- compositions according to the invention are used in the continuous preparation of polyurethane or polyisocyanurate-based metal panels.
- the foaming mixture is applied to the lower metal layer in a Doppelbandlaminator at Bandgeschwindikeiten a maximum of 25 m / min via a traversing mixing head.
- the metal cover layers are profiled here.
- the rising mixture then reaches the top surface layer resulting in a continuously formed layer Metal panel is formed, which is cut at the exit end of the laminator to the desired length.
- the foaming mixture must cover the often profiled cover layers completely and fill the space between the cover layers completely.
- the foaming mixture of a mixing head is dosed here at which a so-called Giessharfe can be.
- Giessharfe the mixture of several openings along the tape direction is discharged.
- the mixing head is traversingly moved across the width of the panel.
- a further task here consists of avoiding surface defects, which here can result from coatings on the metal coating layers (coil coatings), since these often contain defoamers, which can be detrimental to the foam or foaming.
- the compositions according to the invention show advantages in terms of surface qualities, since there are fewer foam defects than when using polyethersiloxanes according to the prior art.
- compositions according to the invention are used in the continuous production of polyurethane or polyisocyanurate-based panels with flexible cover layers.
- the foaming mixture is applied to the lower cover layer in a Doppelbandlaminator at belt speeds of up to about 50 m / min via one or more mixing heads.
- the rising mixture then reaches the upper cover layer, resulting in a continuously formed panel which is cut to the desired length at the exit end of the laminator.
- cover layers such as paper, aluminum, bitumen, fiber flow, multilayer films of various materials, etc.
- the foaming mixture must flow as evenly as possible in a short time due to the higher belt speeds, so that a homogeneous foam without compaction and irregular cell size distribution can occur. Due to the high discharge rates, which are needed here, plants can be used here with more than one mixing head, in which case the foaming mixture is discharged in several strands on the laminator. This process is also known as "finger lay down".
- compositions according to the invention show advantages in terms of surface qualities, since there are fewer foam defects than when using polyethersiloxanes according to the prior art.
- FIG. 1a to 1c show images of foams prepared using the polyethersiloxane according to the invention ( Fig. 1a ) or using polyether siloxanes of the prior art ( Fig. 1b and 1c ) were obtained.
- the polyethersiloxanes indicated in Table 2 were prepared.
- the data in Table 2 are based on formula (I).
- the structural description of the polyether radicals R indicates the sequence of the alkylene oxide building blocks contained in accordance with the block sequence controlled via a sequential metering of the alkylene oxides in the preparation of the polyethers.
- Table 2 produced polyether siloxanes according to the invention ⁇ / u> Bez.
- the hydrosilylation reaction (reactions of the Si-H-functional siloxane with the allyl polyethers) was carried out according to Example 1 in the document EP 1 520 870 carried out.
- 291.0 g (0.1 mol) of the siloxane from Example 1a were reacted with 430.3 g (0.7 mol) of the polyether from Example 1b.
- the comparative foams were carried out by hand mixing. These were polyol, flame retardants, catalysts, water, conventional or inventive foam stabilizer and blowing agents in Weighed a beaker and mixed with a paddle stirrer (6 cm diameter) for 30 s at 1000 rpm. By reweighing, the amount of blowing agent evaporated during the mixing process was determined and supplemented again. Now, the MDI was added, the reaction mixture stirred with the described stirrer at 3000 rpm for 5 seconds and immediately transferred to a thermostated aluminum mold lined with polyethylene film. Mold temperature and geometry varied depending on the foam formulation. The amount of foam formulation used was such that it was 15% above the amount required for the minimum filling of the mold.
- the foams were analyzed. Surface and internal disturbances were assessed subjectively on a scale of 1 to 10, with 10 representing undisturbed foam and 1 extremely disturbed foam.
- the pore structure (average number of cells per 1 cm) was assessed optically on a cut surface by comparison with comparative foams.
- the thermal conductivity was measured on 2.5 cm thick disks with a Hesto Lambda Control instrument at temperatures of 10 ° C and 36 ° C at the top and bottom of the sample.
- the percentage by volume of closed cells was determined using an instrument of the AccuPyc 1330 type from Micromeritics.
- the compression hardnesses of the foams were measured on cube-shaped test specimens with 5 cm edge length according to DIN 53421 up to a compression of 10% (stated is the maximum compressive stress which has occurred in this measuring range).
- Example 2a rigid polyurethane foam system for insulation of refrigerated cabinets
- a formulation adapted for this field of application was used (see Table 3), each containing three polyethersiloxane foam stabilizers according to the invention (PES I, PES II and PES III) and two non-inventive polyether siloxane foam stabilizers (Tegostab B 1048, an exclusively butyl-capped polyether siloxane without free OH groups, and Tegostab B 8408, an OH-functional polyether siloxane with more than 60% primary OH groups , both from the company Evonik Goldschmidt GmbH) was foamed.
- the reaction mixture was introduced into a thermostated at 45 ° C aluminum mold of 145 cm x 14.5 cm x 3.5 cm in size.
- Example 2 Formulation for Example 2a component weight proportion Daltolac R 471 * 100 parts N, N-dimethylcyclohexylamine 1.5 parts water 2.6 parts cyclopentane 13.1 parts polyether 1.5 parts Desmodur 44V20L ** 198.5 parts Polyether polyol from Huntsman ** polymeric MDI from Bayer, 200 mPa * s, 31.5 wt .-% NCO, functionality 2.7
- Example 2b PUR rigid foam system for metal composite elements
- Fig. 1a shows a picture of the surface obtained using the polyethersiloxane PES IV according to the invention.
- the Fig. 1b and 1c show photographs of the surfaces which are prepared using the polyethersiloxane B 8443 ( Fig. 1b ) or B 8486 ( Fig. 1c ) were obtained.
- the polyethersiloxane PES IV according to the invention shows a significant reduction in voids formation and consequently offers better surface quality than the comparative products.
- Table 6 Results on metal composite element stabilizer Defects above / below / inside (1-10) Cells / cm ⁇ -value [mW / m * K] Closed cells [%] PES IV 7 / ** / 8 45-50 22.0 91 B 8443 * 7 / ** / 8 45-50 22.3 94 B 8486 * 7 / ** / 7 40-44 23.0 93 * Comparative examples according to the invention; TEGOSTAB B 8443 and TEGOSTAB B 8486 are polyethersiloxane foam stabilizers from Evonik Goldschmidt GmbH ** show the foam quality of the underside after removing the sheet Fig. 1a to 1c ,
- Example 2c PIR hard foam system for insulation board
- a formulation adapted for this field of application was used (see Table 7), each containing a polyethersiloxane foam stabilizer according to the invention (PES V) and two non-inventive polyethersiloxane foam stabilizers (Tegostab B 1048, an exclusively butyl-capped polyethersiloxane without free OH groups and Tegostab B 8466, an OH-functional polyether siloxane with only primary OH groups, both from Evonik Goldschmidt GmbH) was foamed.
- the reaction mixture was introduced into a thermostated at 50 ° C aluminum mold of 50 cm x 25 cm x 5 cm in size.
- Table 7 Formulations for insulation board component weight proportion Stepanpol PS 2352 * 100 parts Tris (1-chloro-2-propyl) phosphate 15 parts N, N, N ', N ", N" -pentamethyldiethylenetriamine 0.2 parts Potassium octoate (75% by weight in diethylene glycol) 4.0 parts water 0.4 parts n-pentane 20 parts polyether 2.0 parts Desmodur 44V20L ** 200 parts * Polyesterpolyol from Stepan ** polymeric MDI from Bayer, 200 mPa * s, 31.5 wt .-% NCO, functionality 2.7
- Table 8 shows that the foams produced using the polyethersiloxane according to the invention have lower thermal conductivities and a better foam quality at the bottom than the foams obtained using the two comparative products not according to the invention.
- Table 8 Results for insulation board stabilizer Defects above / below / inside (1-10) Cells / cm ⁇ -value [mW / m * K] Closed cell [%] PES V 6/8/8 45-50 22.5 94 B 1048 * 6/7/8 45-50 23.0 92 B 8466 * 6/7/8 45-50 22.8 94 * Comparative examples according to the invention; TEGOSTAB B 1048 and TEGOSTAB B 8466 are polyethersiloxane foam stabilizers from Evonik Goldschmidt GmbH
Abstract
Description
Gegenstand der Erfindung sind Polyethersiloxane und deren Verwendung als Schaumstabilisatoren bei der Herstellung von Polyurethan- bzw. Polyisocyanurat-Schaumstoffen, insbesondere Hartschaumstoffen, welche besonders vorteilhafte Gebrauchseigenschaften, wie niedrige Wärmeleitfähigkeit und insbesondere eine gute Oberflächenqualität, bieten.The invention relates to polyethersiloxanes and their use as foam stabilizers in the production of polyurethane or polyisocyanurate foams, in particular rigid foams, which offer particularly advantageous performance properties, such as low thermal conductivity and in particular a good surface quality.
Bei der Herstellung von Polyurethan- und Polyisocyanurat-Hartschaumstoffen werden zellstabilisierende Additive eingesetzt, welche für eine feinzellige, gleichmäßige und störungsarme Schaumstruktur sorgen sollen und damit die Gebrauchseigenschaften, besonders das thermische Isolationsvermögen, des Hartschaumstoffes im wesentlichen Maße positiv beeinflussen. Besonders effektiv sind Tenside auf der Basis von Polyether-modifizierten Siloxanen, welche daher den bevorzugten Typ der Schaumstabilisatoren darstellen.In the production of rigid polyurethane and polyisocyanurate foams cell stabilizing additives are used, which should provide a fine-celled, uniform and low-interference foam structure and thus the performance characteristics, especially the thermal insulation capacity, of the rigid foam substantially positive influence. Particularly effective are surfactants based on polyether-modified siloxanes, which are therefore the preferred type of foam stabilizers.
Da es eine Vielzahl verschiedener Hartschaumformulierungen für unterschiedliche Anwendungsgebiete gibt, die individuelle Anforderungen an den Schaumstabilisator stellen, werden Polyethersiloxane unterschiedlicher Struktur eingesetzt. Eines der Auswahlkriterien für den Schaumstabilisator ist dabei das in der Hartschaumformulierung enthaltene Treibmittel.Since there are a variety of different rigid foam formulations for different applications, which make individual demands on the foam stabilizer, polyether siloxanes of different structures are used. One of the selection criteria for the foam stabilizer is the propellant contained in the rigid foam formulation.
Verschiedene Veröffentlichungen bezüglich Polyethersiloxan-Schaumstabilisatoren für Hartschaum-Anwendungen wurden bereits publiziert. Die
Die nächste Generation der Fluorchlorkohlenwasserstoff-Treibmittel sind so genannte Hydrochlorfluorkohlenwasserstoffe, wie z. B. HCFC-123. Bei der Verwendung dieser Treibmittel für die Polyurethan-Hartschaum-Herstellung eignen sich laut
Die
Bei der Herstellung von Polyurethan-Hartschäumen mit reinen Fluorkohlenwasserstoffen, wie z. B. Freon, als Treibmittel können laut E P 0 293 125 B1 auch Mischungen unterschiedlicher Stabilisatoren verwendet werden, so zum Beispiel die Kombination eines rein organischen (Siliconfreien) Tensids mit einem Polyethersiloxan.In the production of rigid polyurethane foams with pure fluorocarbons, such. B. Freon, as propellants E P 0 293 125 B1 also mixtures of different stabilizers can be used, such as the combination of a purely organic (silicone-free) surfactant with a polyether siloxane.
Die neuere Entwicklung bei der Herstellung von Polyurethan-Hartschäumen besteht darin, ganz auf halogenierte Kohlenwasserstoffe als Treibmittel zu verzichten und stattdessen Kohlenwasserstoffe wie Pentan einzusetzen. So beschreibt die
In
In
Die in diesen Schriften beschriebenen Schaumstabilisatoren bieten jedoch nicht in der vollen Bandbreite der verschiedenen Hartschaumstoff-Formulierungen die angestrebten optimalen Schaumeigenschaften und in vielen Einsatzgebieten sind Verbesserungen der Schaumstabilisatoren gegenüber dem Stand der Technik wünschenswert, um die Gebrauchseigenschaften der Hartschaumstoffe weiter zu optimieren, insbesondere hinsichtlich der Wärmeleitfähigkeit und der Schaumdefekte an der Oberfläche.However, the foam stabilizers described in these documents do not offer the desired optimum foaming properties in the full range of different rigid foam formulations, and improvements in foam stabilizers over the prior art are desirable in many applications in order to further optimize the performance properties of the rigid foams, in particular with regard to thermal conductivity and the foam defects on the surface.
Gerade die Schaumdefekte an der Oberfläche rücken zunehmend in den Fokus der Betrachtung. Bei Kühlschränken und Metallverbundelementen (Wand-Elemente für den Bau von Gebäuden) beispielsweise, bei denen Polyurethanschaum mit Deckschichten aus Stahlblech verarbeitet wird, können sich direkt unter der Deckschicht liegende Lunker im Schaum auf der Deckschicht-Oberfläche in Form von Beulen oder Blasen abzeichnen und so dem Betrachter einen schlechten Qualitäts-Eindruck vermitteln. Neben dem optischen Eindruck leiden aber auch die physikalischen Eigenschaften unter diesen Schaumdefekten: die Deckschicht-Haftung und die Wärmedämmung verschlechtern sich in der Regel in ihren initialen Werten und können zudem auch einer verstärkten Alterung unter weiterer Verschlechterung der Werte unterliegen. Dieses Problem ist auch bei Polyurethan- bzw. Polyisocyanurat-Dämmplatten bekannt.Especially the foam defects on the surface are increasingly becoming the focus of attention. For example, in refrigerators and metal composite elements (wall elements for building construction) in which polyurethane foam is processed with steel sheet overlays, voids or bubbles lying directly under the cover layer may form in the foam on the topcoat surface in the form of dents or blisters and so on give the viewer a bad quality impression. In addition to the visual impression but also suffer the physical properties of these foam defects: the top layer adhesion and thermal insulation usually deteriorate in their initial values and can also be subject to increased aging with further deterioration of the values. This problem is also known in polyurethane or polyisocyanurate insulation boards.
Das Ausmaß an oberflächennahen Schaumdefekten kann sehr effizient durch die Wahl des Schaumstabilisators beeinflusst werden. Polyethersiloxane mit sogenannten endverkappten Polyether-Seitengruppen, d.h. Polyethern, die anstelle einer OH-Gruppe eine endständige Alkylether- oder Ester-Gruppe aufweisen, sind für vergleichsweise störungsarme Oberflächenqualitäten bekannt. Leider sind diese Schaumstabilisatoren schlechter in Polyol-Formulierungen löslich als OH-funktionelle Produkte. Der Einsatz von unlöslichen Schaumstabilisatoren in vorformulierten Polyol-Systemen, wie sie insbesondere für die Einsatzgebiete Kühlschrank-Isolation und Metallverbundelemente marktüblich sind, verbietet sich durch die Gefahr einer Phasenseparation der Formulierung während längerer Lagerzeiten vor der Verarbeitung. Aus diesem Grund ist der Einsatz von vollständig endverkappten Schaumstabilisatoren zur Verbesserung der Oberflächenqualität insbesondere bei Kühlschrank-Anwendungen, aber auch in vielen anderen Anwendungsgebieten, nicht oder nur eingeschränkt möglich. Es besteht deshalb die Aufgabe, alternative Schaumstabilisatoren bereitzustellen, die die Herstellung von Polyurethan- bzw. Polyisocyanurat-Schaumstoffen mit guter Oberflächenqualität - insbesondere wenig Lunkern und Verdichtungen im Kontaktbereich mit Deckschichten - ermöglichen, ohne einen oder mehrere der aus dem Stand der Technik bekannten Nachteile, wie z.B. schlechte Systemlöslichkeit, aufzuweisen.The extent of near-surface foam defects can be very efficiently influenced by the choice of foam stabilizer. Polyether siloxanes with so-called end-capped polyether side groups, ie polyethers, which instead of an OH group, a terminal alkyl ether or Ester group are known for relatively low-surface quality. Unfortunately, these foam stabilizers are less soluble in polyol formulations than OH-functional products. The use of insoluble foam stabilizers in pre-formulated polyol systems, which are customary in the market, especially for the areas of refrigerator insulation and metal composite elements, is precluded by the risk of phase separation of the formulation during longer storage times before processing. For this reason, the use of fully end-capped foam stabilizers to improve the surface quality, especially in refrigerator applications, but also in many other applications, not or only partially possible. It is therefore an object to provide alternative foam stabilizers which allow the production of polyurethane or polyisocyanurate foams having good surface quality - in particular little voids and densities in the contact area with cover layers - without one or more of the disadvantages known from the prior art, such as poor system solubility.
Eine bevorzugte Aufgabe der Erfindung war weiterhin die Entwicklung von Polyurethan- bzw. Polyisocyanurat-Hartschaumstoffen und den ihnen zugrunde liegenden Formulierungen, welche besonders vorteilhafte Gebrauchseigenschaften, wie z. B. gute Oberflächenqualität und/oder niedrige Wärmeleitfähigkeit, bieten.A preferred object of the invention was also the development of rigid polyurethane or polyisocyanurate foams and their underlying formulations, which have particularly advantageous performance characteristics such. B. good surface quality and / or low thermal conductivity offer.
Überraschenderweise wurde nun gefunden, dass Polyethersiloxane der Formel (I), wie nachfolgend und in den Ansprüchen beschrieben, die kaum primäre sondern überwiegend sekundäre und/oder tertiäre OH-Gruppen aufweisen, eine oder mehrere der vorgenannten Aufgaben lösen. Dies war insbesondere auch deshalb überraschend, da in
Ein Gegenstand der vorliegenden Erfindung sind deshalb Polyethersiloxane der Formel (I), wie nachfolgend und in den Ansprüchen beschrieben, die kaum primäre sondern überwiegend sekundäre oder tertiäre OH-Gruppen aufweisen, und die Verwendung der erfindungsgemäßen Polyethersiloxane zur Herstellung von Polyurethanschaumstoffen und Polyisocyanuratschaumstoffen.An object of the present invention are therefore polyethersiloxanes of the formula (I), as described below and in the claims, which have scarcely primary but predominantly secondary or tertiary OH groups, and the use of the polyethersiloxanes according to the invention for the production of polyurethane foams and Polyisocyanuratschaumstoffen.
Ein weiterer Gegenstand der vorliegenden Erfindung ist eine Zusammensetzung, geeignet zur Herstellung von Polyurethan-oder Polyisocyanurat-Hartschaumstoffen, enthaltend zumindest eine Isocyanatkomponenten, zumindest eine Polyolkomponente, zumindest einen Schaumstabilisator, zumindest einen Urethan- und/oder Isocyanurat-Katalysator, Wasser und/oder Treibmittel, und optional zumindest ein Flammschutzmittel und/oder weitere Additive, welche dadurch gekennzeichnet ist, dass als Schaumstabilisator zumindest ein erfindungsgemäßes Polyethersiloxan enthalten ist, ein Verfahren zur Herstellung von Polyurethan- oder Polyisocyanurat-Hartschaumstoffen, durch Umsetzung dieser Zusammensetzung sowie die dadurch erhältlichen Polyurethan-oder Polyisocyanurat-Hartschaumstoffe.A further subject matter of the present invention is a composition suitable for producing rigid polyurethane or polyisocyanurate foams comprising at least one isocyanate component, at least one polyol component, at least one foam stabilizer, at least one urethane and / or isocyanurate catalyst, water and / or blowing agent , and optionally at least one flame retardant and / or further additives, which is characterized in that at least one polyether siloxane according to the invention is contained as a foam stabilizer, a process for the preparation of rigid polyurethane or polyisocyanurate foams, by reacting this composition and the resulting polyurethane or polyisocyanurate foams.
Außerdem ist Gegenstand der vorliegenden Erfindung die Verwendung von erfindungsgemäßen Polyurethan- oder Polyisocyanurat-Hartschaumstoffen als Dämmplatten, Isolationsmittel und in Form von Metallverbundelementen als Konstruktionselement für den Bau von Gebäuden, Kühlräumen, Kühl-Containern und -Lastkraftwagen sowie eine Kühlapparatur, die als Isoliermaterial einen erfindungsgemäßen Polyurethan- oder Polyisocyanurat-Hartschaumstoff aufweist.In addition, the present invention is the use of rigid polyurethane or polyisocyanurate foams of the invention as insulation boards, insulation and in the form of metal composite elements as Construction element for the construction of buildings, cold rooms, refrigerated containers and trucks and a cooling apparatus, which has a polyurethane or polyisocyanurate rigid foam according to the invention as an insulating material.
Die erfindungsgemäßen Polyethersiloxane haben den Vorteil, dass mit Ihnen Polyurethan- oder Polyisocyanuratschäume, insbesondere Hartschäume hergestellt werden können, die sich durch eine gute Feinzelligkeit und gute Isoliereigenschaften auszeichnen und gleichzeitig wenig Schaumdefekte aufweisen. Insbesondere die bei Composit-Systemen aus Hartschaumstoff mit flexiblen oder starren Deckschichten problematischen Schaumdefekte (Lunker, Verdichtungen) an der Grenzfläche zur Deckschicht lassen sich mithilfe der erfindungsgemäßen Polyethersiloxane wirksam gegenüber dem Stand der Technik minimieren.The polyethersiloxanes of the invention have the advantage that polyurethane or Polyisocyanuratschäume, in particular rigid foams can be produced with you, which are characterized by good fineness and good insulating properties and at the same time have little foam defects. In particular, the foam defects (voids, densities) problematic in composite systems made of rigid foam with flexible or rigid cover layers at the interface with the cover layer can be effectively minimized with the aid of the polyether siloxanes according to the invention over the prior art.
Die erfindungsgemäßen Polyethersiloxane, Zusammensetzungen und Polyurethanschäume sowie deren Verwendungen werden nachfolgend beispielhaft beschrieben, ohne dass die Erfindung auf diese beispielhaften Ausführungsformen beschränkt sein soll. Sind nachfolgend Bereiche, allgemeine Formeln oder Verbindungsklassen angegeben, so sollen diese nicht nur die entsprechenden Bereiche oder Gruppen von Verbindungen umfassen, die explizit erwähnt sind, sondern auch alle Teilbereiche und Teilgruppen von Verbindungen, die durch Herausnahme von einzelnen Werten (Bereichen) oder Verbindungen erhalten werden können. Werden im Rahmen der vorliegenden Beschreibung Dokumente zitiert, so soll deren Inhalt, insbesondere bezüglich der in Bezug genommenen Sachverhalte vollständig zum Offenbarungsgehalt der vorliegenden Erfindung gehören. Wenn im nachfolgenden Mittelwerte angegeben sind, so handelt es sich, wenn nicht anders angegeben, um das Zahlenmittel.The polyethersiloxanes, compositions and polyurethane foams according to the invention and their uses are described below by way of example, without the invention being restricted to these exemplary embodiments. Given below, ranges, general formulas, or classes of compounds are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be. If documents are cited in the context of the present description, their content, in particular with regard to the matters referred to, should form part of the disclosure content of the present invention. If averages are given below, the number average is, unless stated otherwise.
Die erfindungsgemäßen Polyethersiloxane der Formel (I),
R1- Si (CH3) 2-O- [-Si (CH3)2-O-]n- [-Si (CH3) R-O-]m-Si (CH3) 2-R2
mit
R, R1 und R2 gleich oder verschieden,
R1 und/oder R2 gleich Methyl oder R,
R gleich oder verschieden -(CH2)x-O-(CH2-CR'R''-O)y-R''',
R', R" gleich oder verschieden -H, -CH3, -CH2CH3, oder Phenyl-Rest,
R''' = -H, -Alkyl- oder -Acyl-Rest, vorzugsweise - Alkyl-Rest mit 1 bis 40, bevorzugt 1 bis 24 Kohlenstoffatomen oder -Acyl-Rest mit 1 bis 40, vorzugsweise 1 bis 24 Kohlenstoffatomen,
wobei die Alkylenoxid-Bausteine (CH2-CR'R''-O) innerhalb eines Polyether-Restes R gleich oder unterschiedlich sein können und die Polyether-Reste R innerhalb eines Polyethersiloxan-Moleküls der Formel (I) gleich oder unterschiedlich sein können, dadurch gekennzeichnet, dass im Mittel (Zahlenmittel, gemittelt über alle Verbindungen der Formel (I))
n+m+2 = > 10 bis 200, vorzugsweise 12 bis 100, bevorzugt 15 bis 50 und besonders bevorzugt 20 bis 40,
m = 0 bis 40 für R1 und/oder R2 gleich R
bzw. m = 1 bis 40 für R1 und R2 gleich -CH3,
x = 2 bis 10,
y = 1 bis 50,
wobei mindestens 25%, vorzugsweise mindestens 50%, besonders bevorzugt 100% der Reste R''' gleich Wasserstoff sind und wobei von allen Polyether-Resten R, die eine Endgruppe R'''= -H besitzen, mindestens 50%, bevorzugt mindestens 70%, eine sekundäre oder tertiäre OH-Endgruppe, d.h. einen endständigen Alkylenoxid-Baustein mit R' und/oder R'' ungleich -H, aufweisen.The polyethersiloxanes of the formula (I) according to the invention,
R 1 -Si (CH 3 ) 2 -O- [-Si (CH 3 ) 2 -O-] n - [-Si (CH 3 ) RO-] m -Si (CH 3 ) 2 -R 2
With
R, R 1 and R 2 are the same or different,
R 1 and / or R 2 are methyl or R,
R is the same or different - (CH 2 ) x -O- (CH 2 -CR'R "-O) y -R ''',
R ', R ", equal or different, are -H, -CH 3 , -CH 2 CH 3 , or phenyl radical,
R '"= -H, -alkyl or -acyl radical, preferably -alkyl radical having 1 to 40, preferably 1 to 24, carbon atoms or -acyl radical having 1 to 40, preferably 1 to 24, carbon atoms,
wherein the alkylene oxide building blocks (CH 2 -CR'R "-O) within a polyether radical R may be the same or different and the polyether radicals R may be identical or different within a polyethersiloxane molecule of the formula (I), characterized in that on the average (number average, averaged over all compounds of formula (I))
n + m + 2 => 10 to 200, preferably 12 to 100, preferably 15 to 50 and particularly preferably 20 to 40,
m = 0 to 40 for R 1 and / or R 2 is equal to R
or m = 1 to 40 for R 1 and R 2 is -CH 3 ,
x = 2 to 10,
y = 1 to 50,
wherein at least 25%, preferably at least 50%, particularly preferably 100% of the radicals R '''equal hydrogen and wherein of all polyether radicals R having an end group R''' = -H, at least 50%, preferably at least 70%, a secondary or tertiary OH end group, ie a terminal alkylene oxide unit having R 'and / or R''not equal to -H.
Die erfindungsgemäßen Polyethersiloxane der Formel (I) sind Copolymere, die herstellungsbedingt meist polydisperse Verbindungen sind, so dass hinsichtlich der Parameter n, m, x und y nur Mittelwerte angegeben werden können.The polyether siloxanes of the formula (I) according to the invention are copolymers which are usually polydisperse compounds as a result of the preparation, so that with regard to the parameters n, m, x and y only average values can be stated.
Das Verhältnis von primären zu sekundären/tertiären OH-Gruppen kann z. B. durch die bei der Herstellung verwendeten Polyether oder durch die Menge des eingesetzten Verkappungsreagenzes beeinflusst werden. Das Verhältnis von primären zu sekundären und tertiären OH-Endgruppen kann mittels NMR-Methoden bestimmt werden. Vorzugsweise erfolgt die Bestimmung wie nachfolgend beschrieben mit einem NMR-Spektrometer mit Rechnereinheit und Autosampler mit 5 mm Probenkopf der Firma Bruker, Typ 400 MHz, 10 mm QNP unter Verwendung von 5 mm Probenröhrchen und Verschlußkappen aus Plastik, beides von der Firma Norell Inc. Die Probennahme erfolgt mittels Pasteur-Pipetten der Firma Brand. Als Reagenzien werden eingesetzt: Deuterochloroform (CDCl3) der Firma Deutro, Deuterierungsgrad 99,8 %), Molsieb A3 der Firma Merck (zur Entfernung von Wasserresten aus dem Lösemittel).The ratio of primary to secondary / tertiary OH groups may, for. B. be influenced by the polyether used in the preparation or by the amount of the capping reagent used. The ratio of primary to secondary and tertiary OH end groups can be determined by NMR methods. Preferably, the determination is carried out as described below with a NMR spectrometer with computer unit and autosampler with 5 mm probe head from Bruker, type 400 MHz, 10 mm QNP using 5 mm plastic test tubes and caps, both from Norell Inc. The Sampling takes place using Pasteur pipettes from Brand. Reagents used are: Deuterochloroform (CDCl 3 ) from Deutro, degree of deuteration 99.8%), molecular sieve A3 from Merck (for removal of water residues from the solvent).
Die Messungen werden unter Verwendung der in Tabelle A angegebenen Messparameter durchgeführt:
Dazu wird die angegebene Probenmenge in ein sauberes NMR-Röhrchen eingefüllt und mit dem angegebenen Volumen an CDCl3 versetzt. Das Probenröhrchen wird mit der Plastikkappe verschlossen und die Probe durch Schütteln homogenisiert. Nachdem sich alle Luftbläschen an der Oberfläche abgesetzt haben, wird die Probe im NMR-Spektrometer vermessen. Die Zuordnung der einzelnen Signale ist dem Fachmann geläufig oder kann gegebenenfalls durch Vergleich mit den Signalen geeigneter Beispielsubstanzen erfolgen. Die Auswertung bezüglich der molaren Verhältnisse von freien OH-Gruppen (R'' = H) zu endverkappten OH-Gruppen (R'' ungleich H) erfolgt durch das ins Verhältnis setzen der entsprechenden Integrale der Signale, die den jeweiligen Gruppen zugeordnet sind. Um eine Vergleichbarkeit der Signale zu gewährleisten ist dem Fachmann bekannt, sogenannte Beschleuniger den Proben zuzusetzen. Einen geeigneten Beschleuniger kann der Fachmann durch Vermessen von Modellsubstanzen, bei denen das molare Verhältnis bekannt ist, ermitteln. Geeignete Beschleuniger sind solche, bei denen das gemessene Verhältnis vom tatsächlichen Verhältnis um maximal 5 % abweicht. Als Beschleuniger kann z.B. Chromacetylacetonat, welches in Konzentrationen von ca. 0,8 Massen-% bezogen auf die Probenmenge zugegeben wird, verwendet werden.For this purpose, the specified amount of sample is introduced into a clean NMR tube and mixed with the indicated volume of CDCl 3 . The sample tube is closed with the plastic cap and the sample is homogenized by shaking. After all air bubbles have settled on the surface, the sample is measured in the NMR spectrometer. The assignment of the individual signals is familiar to the person skilled in the art or, if appropriate, can be carried out by comparison with the signals of suitable example substances. The evaluation with respect to the molar ratios of free OH groups (R '' = H) to end-capped OH groups (R '' not equal to H) takes place by the ratio of the corresponding integrals of the signals which are assigned to the respective groups. To ensure comparability of the signals, it is known to the person skilled in the art to add so-called accelerators to the samples. A suitable accelerator can be determined by the person skilled in the art by measuring model substances in which the molar ratio is known. Suitable accelerators are those in which the measured ratio deviates from the actual ratio by a maximum of 5%. For example, chromium acetylacetonate which is added in concentrations of about 0.8% by mass, based on the amount of sample, can be used as the accelerator.
Es kann vorteilhaft sein, wenn sich Polyethersubstituenten in der Kammposition (seitenständig) der Siloxankette befinden (m ungleich 0). Zusätzlich können Polyethersubstituenten an den endständigen Siliziumatomen der Siloxankette vorhanden sein (R1 und/oder R2 = R).It may be advantageous if polyether substituents are in the comb position (lateral) of the siloxane chain (m is not equal to 0). In addition, polyether substituents may be present on the terminal silicon atoms of the siloxane chain (R 1 and / or R 2 = R).
Die Endgruppe der Polyether-Reste ist entweder eine freie OH-Gruppe, eine Alkylether-Gruppe (vorzugsweise Methyl) oder ein Ester, entstanden durch Veresterung der OH-Gruppe mit einer beliebigen Carbonsäure (vorzugsweise Essigsäure). Es kann vorteilhaft sein, wenn ein Teil der Reste R''' Akylreste, vorzugsweise ausschließlich Methylreste sind, erfindungswesentlich ist jedoch, dass im Mittel (Zahlenmittel, gemittelt über alle Verbindungen der Formel (I)) mindestens 25% der Polyether eine OH-Endgruppe tragen (d.h. R''' = -H) und diese OH-Gruppen überwiegend (mind. 50 %) sekundäre oder tertiäre OH-Gruppen sind.The end group of the polyether radicals is either a free OH group, an alkyl ether group (preferably methyl) or an ester formed by esterification of the OH group with any carboxylic acid (preferably acetic acid). It may be advantageous if a part of the radicals R ''' Akylreste, preferably exclusively methyl radicals are essential to the invention, however, that on average (number average, averaged over all compounds of formula (I)) at least 25% of the polyethers carry an OH end group (ie R '''= -H) and this OH Groups are predominantly (at least 50%) secondary or tertiary OH groups.
Bei den mit dem Index y bezeichneten Alkylenoxid-Einheiten handelt es sich bevorzugt um Ethylenoxid, Propylenoxid, n-Butylenoxid, iso-Butylenoxid und Styroloxid. Der Stoffmengenanteil an Ethylenoxid beträgt vorzugsweise mindestens 45 mol-%, besonders bevorzugt mindestens 65 mol-%.The alkylene oxide units denoted by the index y are preferably ethylene oxide, propylene oxide, n-butylene oxide, isobutylene oxide and styrene oxide. The mole fraction of ethylene oxide is preferably at least 45 mol%, more preferably at least 65 mol%.
Die Sequenz der verschiedenen Alkylenoxid-Bausteine kann - abgesehen von dem Endblock bei OH-funktionellen Polyethern - beliebig sein, d.h. sie kann entweder statistische sein, oder einem gezielten Blockaufbau unterliegen. Bei OH-funktionellen Polyether-Resten kann ein Di-Block-Aufbau, bestehend aus einem reinen Ethylenoxid-Block und dem abschließenden Endblock aus einem Alkylenoxid ungleich Ethylenoxid, besonders vorteilhaft sein.The sequence of the various alkylene oxide building blocks may be arbitrary, other than the endblock in OH-functional polyethers, i. it can either be statistical or subject to targeted block building. In the case of OH-functional polyether radicals, a di-block structure consisting of a pure ethylene oxide block and the terminal end block of an alkylene oxide other than ethylene oxide may be particularly advantageous.
Die Polyether in einem Molekül können untereinander gleich oder verschieden sein, sofern die Polyethermischung die obigen Definitionen erfüllt. Ferner sind auch Mischungen verschiedener Polyethersiloxane eingeschlossen, sofern entweder die Mittelwerte der Mischung in die o. g. Bereiche fallen oder eine Komponente der obigen Definition entspricht.The polyethers in a molecule may be the same or different from each other as long as the polyether mixture satisfies the above definitions. Furthermore, mixtures of different polyether siloxanes are also included, provided that either the mean values of the mixture in the o. Areas fall or corresponds to a component of the above definition.
Besonders bevorzugte erfindungsgemäße Polyethersiloxane sind solche, bei denen im Mittel n+m+2 gleich 15 bis 100, x gleich 3 und y gleich 5 bis 25 ist und R1 sowie R2 Polyether-Reste vom Typ R sind.Particularly preferred polyether siloxanes according to the invention are those in which on average n + m + 2 is equal to 15 to 100, x is 3 and y is 5 to 25 and R 1 and R 2 are polyether radicals of the R type.
Die Polyethersiloxane gemäß der vorliegenden Erfindung können prinzipiell nach den aus dem Stand der Technik bekannten Verfahren zur Herstellung von Polyethersiloxanen erhalten werden.The polyethersiloxanes according to the present invention can in principle be obtained according to the processes known from the prior art for the preparation of polyethersiloxanes.
Die Synthese der erfindungsgemäßen Polyethersiloxane erfolgt vorzugsweise durch eine Platin-katalysierte Umsetzung von Si-H-funktionellen Siloxanen mit endständig ungesättigten Polyethern. Eine detaillierte Beschreibung findet sich in
Die in dieser sogenannten Hydrosilylierungsreaktion eingesetzten Vorstufen sind ihrerseits mit Hilfe von etablierten chemischen Verfahren zugänglich:
- Die Si-H-funktionellen Siloxane können durch Umsetzung von SiH-Funktion-freien Siloxanen , vorzugsweise z.B. Hexamethyldisiloxan und Decamethylcyclopentasiloxan, mit Si-H-funktionellen Siloxanen, vorzugsweise linearen Polymethylhydrogensiloxanen, wie beispielsweise HMS-993 der Firma Gelest Inc., und optional linearen α,ω-Dihydrogenpolydimethylsiloxanen, wie beispielsweise 1,1,3,3-Tetramethyldisiloxan, in einer Säure-katalysierten Äquilibrierungsreaktion erhalten werden. Die mittlere Struktur des Produktes wird dabei über das Verhältnis der eingesetzten Rohstoffe bestimmt.
- The Si-H-functional siloxanes can be prepared by reacting SiH-function-free siloxanes, preferably eg hexamethyldisiloxane and decamethylcyclopentasiloxane, with Si-H-functional siloxanes, preferably linear polymethylhydrogensiloxanes, such as HMS-993 from Gelest Inc., and optionally linear α, ω-dihydrogenpolydimethylsiloxanes, such as 1,1,3,3-tetramethyldisiloxane, are obtained in an acid catalyzed equilibration reaction. The mean structure of the product is determined by the ratio of the raw materials used.
Die endständig ungesättigten Polyether können durch Umsetzung von endständig ungesättigten Startalkoholen, wie vorzugsweise Allylalkohol, mit verschiedensten Alkylenoxiden erhalten werden, vorzugsweise unter alkalischer Katalyse mit beispielsweise Alkalihydroxiden oder Doppelmetallcyanid-Katalyse (DMC-Katalyse). Die Sequenz der erhaltenen Polyether wird dabei über die Dosierung der Alkylenoxide gesteuert. Block-Strukturen können dadurch erhalten werden, dass zunächst Alkylenoxid A an den Startalkohol angelagert wird und nach Erreichen eines vollständigen Umsatzes das Alkylenoxid B zudosiert und angelagert wird. Statistische Sequenzen können dadurch erhalten werden, dass die Alkylenoxide A und B im Gemisch eingesetzt werden. Sind die gewünschte Sequenz und Molmasse aufgebaut, können die Polyether gegebenenfalls entweder direkt einer wässrigen Aufarbeitung unterzogen werden, wobei Produkte mit endständiger OH-Funktion erhalten werden, oder optional einem weiteren Reaktionsschritt zur Endverkappung unterzogen werden, beispielsweise durch Umsetzung mit Methylchlorid unter Bildung einer Methylether-Endgruppe nach Williamson. So ist zum Beispiel in
Um den erfindungsgemäßen Anteil an sekundären oder tertiären OH-Endgruppe zu erhalten, können verschiedene Methoden angewandt werden. Eine Möglichkeit besteht z. B. darin, dass bei der Herstellung der Polyether abschließend ein Block aus im Mittel 0,5 bis 5, vorzugsweise 1 bis 3 Alkylenoxid-Baustein pro Polyethermolekül mit R' und/oder R'' ungleich -H angelagert wird. Geeignete Alkylenoxide für diesen Endblock sind beispielsweise Propylenoxid, Butylenoxid, iso-Butylenoxid und Styroloxid.In order to obtain the proportion of secondary or tertiary OH end group according to the invention, various methods can be used. One way is z. B. is that in the preparation of the polyether finally a block of on average from 0.5 to 5, preferably 1 to 3 alkylene oxide block per polyether molecule with R 'and / or R' 'is added not equal to -H. Suitable alkylene oxides for this end block are, for example, propylene oxide, butylene oxide, isobutylene oxide and styrene oxide.
Abgesehen von dem beschriebenen Endblock bei OH-funktionellen Polyethern können verschiedenste Alkylenoxide zur Herstellung der Polyether-Reste verwendet werden, bevorzugt sind Ethylenoxid, Propylenoxid, optional Butylenoxid und optional Styroloxid. Dabei sollte, gemittelt über alle Polyether-Reste in allen Molekülen gemäß Formel (I), der Stoffmengenanteil an Ethylenoxid vorzugsweise mindestens 45 mol-%, besonders bevorzugt mindestens 65 %, betragen. Die Sequenz der verschiedenen Alkylenoxid-Bausteine kann - abgesehen von dem Endblock bei OH-funktionellen Polyethern - beliebig gewählt werden, d.h. sie kann entweder durch statistischen Einbau erhalten werden, oder durch einen gezielten Blockaufbau erhalten werden. Insbesondere bei den OH-funktionellen Polyether-Resten kann es vorteilhaft sein, wenn ein Di-Block-Aufbau erzielt wird, wobei zunächst ein reiner Ethylenoxid-Block erzeugt wird und anschließend der abschließende Endblock, in dem abschließend ein Alkylenoxid ungleich Ethylenoxid eingesetzt wird.Apart from the described endblock in OH-functional polyethers, a wide variety of alkylene oxides can be used to prepare the polyether residues. preferred are ethylene oxide, propylene oxide, optionally butylene oxide and optionally styrene oxide. In this case, averaged over all polyether radicals in all molecules according to formula (I), the mole fraction of ethylene oxide should preferably be at least 45 mol%, more preferably at least 65%. The sequence of the various alkylene oxide building blocks can be chosen arbitrarily, apart from the endblock in the case of OH-functional polyethers, ie they can be obtained either by random incorporation or obtained by a targeted block construction. In particular, in the OH-functional polyether residues, it may be advantageous if a di-block structure is achieved, wherein initially a pure ethylene oxide block is produced and then the final end block, in which an alkylene oxide is used unlike ethylene oxide.
Die erfindungsgemäßen Polyethersiloxane können in allen bekannten Anwendungen, bei denen Polyethersiloxane eingesetzt werden, verwendet werden. Vorzugsweise werden die erfindungsgemäßen Polyethersiloxane zur Herstellung von Polyurethanschaumstoffen, Polyisocyanuratschaumstoffen, insbesondere zur Herstellung von Polyurethan- oder Polyisocyanurat-Hartschaumstoffen verwendet.The polyethersiloxanes according to the invention can be used in all known applications in which polyethersiloxanes are used. The polyethersiloxanes according to the invention are preferably used for the production of polyurethane foams, polyisocyanurate foams, in particular for the production of rigid polyurethane or polyisocyanurate foams.
Die erfindungsgemäßen Zusammensetzungen (meist aufgeteilt in zwei Komponenten), die zur Herstellung von Polyurethan-oder Polyisocyanurat-Hartschaumstoffen geeignet sind, enthalten zumindest eine Isocyanatkomponenten, zumindest eine Polyolkomponente, zumindest einen Schaumstabilisator, zumindest einen Urethan- und/oder Isocyanurat-Katalysator, optional Wasser und/oder Treibmittel, und optional zumindest ein Flammschutzmittel und/oder weitere Additive, und zeichnen sich dadurch aus, dass sie als Schaumstabilisator zumindest ein erfindungsgemäßes Polyethersiloxan bzw. ein Polyethersiloxan-Gemisch, welches erfindungsgemäße Polyethersiloxane aufweist bzw. daraus besteht, enthalten. Ist die erfindungsgemäße Zusammensetzung vor der Verarbeitung in zwei oder mehr Komponenten aufgeteilt, so ist das erfindungsgemäße Polyethersiloxan bzw. Polyethersiloxan-Gemisch vorzugsweise nicht in der Komponente enthalten, die die Isocyanatkomponente enthält.The compositions according to the invention (usually divided into two components) which are suitable for producing rigid polyurethane or polyisocyanurate foams comprise at least one isocyanate component, at least one polyol component, at least one foam stabilizer, at least one urethane and / or isocyanurate catalyst, optionally water and / or propellant, and optionally at least one flame retardant and / or other additives, and are characterized in that they as foam stabilizer at least one inventive polyether siloxane or a polyether siloxane mixture, which According to the invention comprises or consists of polyether siloxanes. If the composition according to the invention is divided into two or more components before processing, the polyethersiloxane or polyethersiloxane mixture according to the invention is preferably not present in the component which contains the isocyanate component.
In der erfindungsgemäßen Zusammensetzung beträgt der Massenanteil an erfindungsgemäßen Polyethersiloxan (als Schaumstabilisatoren) bezogen auf 100 Massenteile Polyolkomponente (pphp) vorzugsweise von 0,1 bis 10 pphp, bevorzugt 0,5 bis 5 pphp und besonders bevorzugt bei 1 bis 3 pphp.In the composition according to the invention, the mass fraction of polyethersiloxane according to the invention (as foam stabilizers) based on 100 parts by mass of polyol component (pphp) is preferably from 0.1 to 10 pphp, preferably 0.5 to 5 pphp and particularly preferably 1 to 3 pphp.
Als Isocyanatkomponente kann die erfindungsgemäße Zusammensetzung alle zur Herstellung von Polyurethan- oder Polyisocyanurat-Hartschaumstoffen geeigneten Isocyanatverbindungen aufweisen. Vorzugsweise weist die erfindungsgemäße Zusammensetzung ein oder mehrere organische Isocyanate mit zwei oder mehr Isocyanat-Funktionen auf, wie beispielsweise 4, 4'-Diphenylmethandiisocyanat (MDI), Toluoldiisocyanat (TDI), Hexamethylendiisocyanat (HMDI) und Isophorondiisocyanat (IPDI). Besonders geeignet ist das als "polymeres MDI" ("crude MDI") bekannte Gemisch aus MDI und höher kondensierten Analogen mit einer mittleren Funktionalität von 2 bis 4, sowie die verschiedenen Isomere des TDI in reiner Form oder als Isomerengemisch.As isocyanate component, the composition according to the invention may comprise all isocyanate compounds suitable for the preparation of rigid polyurethane or polyisocyanurate foams. Preferably, the composition according to the invention comprises one or more organic isocyanates having two or more isocyanate functions, such as 4,4'-diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI) and isophorone diisocyanate (IPDI). Particularly suitable is the mixture known as "polymeric MDI" ("crude MDI") of MDI and higher condensed analogues having an average functionality of 2 to 4, and the various isomers of TDI in pure form or as a mixture of isomers.
Geeignete Polyole im Sinne dieser Erfindung können alle organischen Substanzen mit mehreren gegenüber Isocyanaten reaktiven Gruppen, sowie deren Zubereitungen sein. Bevorzugte Polyole sind alle zur Herstellung von Polyurethan-Schaumstoffen üblicherweise verwendeten Polyetherpolyole und Polyesterpolyole. Polyetherpolyole können durch Umsetzung von mehrwertigen Alkoholen oder Aminen mit Alkylenoxiden gewonnen werden. Polyesterpolyole basieren auf Estern mehrwertiger Carbonsäuren (die entweder aliphatisch, beispielsweise Adipinsäure, oder aromatisch, beispielsweise Phthalsäure oder Terephthalsäure, sein können) mit mehrwertigen Alkoholen (meist Glycolen).Suitable polyols for the purposes of this invention may be all organic substances having a plurality of isocyanate-reactive groups, as well as their preparations. Preferred polyols are all polyether polyols and polyester polyols commonly used to make polyurethane foams. polyether polyols can be obtained by reaction of polyhydric alcohols or amines with alkylene oxides. Polyester polyols are based on esters of polybasic carboxylic acids (which may be either aliphatic, for example adipic acid or aromatic, for example phthalic acid or terephthalic acid) with polyhydric alcohols (usually glycols).
Ein geeignetes Verhältnis von Isocyanat und Polyol, ausgedrückt als Index der Formulierung, d.h. als stöchiometrisches Verhältnis von Isocyanat-Gruppen zu gegenüber Isocyanat reaktiven Gruppen (z.B. OH-Gruppen, NH-Gruppen) multipliziert mit 100, liegt im Bereich von 10 bis 1000, bevorzugt 80 bis 350.A suitable ratio of isocyanate and polyol, expressed as the index of the formulation, i. the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g., OH groups, NH groups) multiplied by 100 is in the range of 10 to 1,000, preferably 80 to 350.
Als Urethan- und/oder Isocyanurat-Katalysatoren weist die erfindungsgemäße Zusammensetzung vorzugsweise ein oder mehrere Katalysatoren für die Reaktionen Isocyanat-Polyol und/oder Isocyanat-Wasser und/oder die Di- bzw. Trimerisierung des Isocyanates auf. Typische Beispiele sind die Amine Triethylamin, Dimethylcyclohexylamin, Tetramethylethylendiamin, Tetramethylhexandiamin, Pentamethyldiethylentriamin, Pentamethyldipropylentriamin, Triethylendiamin, Dimethylpiperazin, 1,2-Dimethylimidazol, N-Ethylmorpholin, Tris(dimethylaminopropyl)hexahydro-1,3,5-triazin, Dimethylaminoethanol, Dimethylaminoethoxyethanol und Bis(dimethylaminoethyl)ether, Zinnverbindungen wie Dibutylzinndilaurat oder Zinn-II-2-ethylhexanoat und Kaliumsalze wie Kaliumacetat und Kalium-2-ethylhexanoat.As urethane and / or isocyanurate catalysts, the composition according to the invention preferably comprises one or more catalysts for the reactions isocyanate-polyol and / or isocyanate-water and / or the di- or trimerization of the isocyanate. Typical examples are the amines triethylamine, dimethylcyclohexylamine, tetramethylethylenediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenediamine, dimethylpiperazine, 1,2-dimethylimidazole, N-ethylmorpholine, tris (dimethylaminopropyl) hexahydro-1,3,5-triazine, dimethylaminoethanol, dimethylaminoethoxyethanol and bis (Dimethylaminoethyl) ether, tin compounds such as dibutyltin dilaurate or tin II-2-ethylhexanoate and potassium salts such as potassium acetate and potassium 2-ethylhexanoate.
Bevorzugte in der erfindungsgemäßen Zusammensetzung vorhandene Mengen an Katalysatoren richten sich nach dem Typ des Katalysators und liegen üblicherweise im Bereich von 0,05 bis 5 pphp (= Massenteile bezogen auf 100 Massenteile Polyol) bzw. 0,1 bis 10 pphp für Kaliumsalze. Geeignete Wasser-Gehalte im Sinne dieser Erfindung hängen davon ab, ob zusätzlich zum Wasser noch ein oder mehrere Treibmittel eingesetzt werden oder nicht. Bei rein Wasser getriebenen Schäumen liegen die Werte typischerweise bei 1 bis 20 pphp, werden zusätzlich andere Treibmittel eingesetzt, verringert sich die Einsatzmenge auf üblicherweise 0 bis 5 pphp.Preferred amounts of catalysts present in the composition of the invention depend on the type of catalyst and are usually in the range of 0.05 to 5 pphp (= parts by mass based on 100 parts by mass of polyol) or 0.1 to 10 pphp for potassium salts. Suitable water contents in the context of this invention depend on whether one or more propellants are used in addition to the water or not. In the case of pure water-driven foams, the values are typically from 1 to 20 pphp, if other blowing agents are additionally used, the amount of use is reduced to usually 0 to 5 pphp.
Sind in der erfindungsgemäßen Zusammensetzung zusätzliche Treibmittel vorhanden, können diese physikalische oder chemische Treibmittel sein. Vorzugsweise weist die Zusammensetzung physikalische Treibmittel auf. Geeignete physikalische Treibmittel im Sinne dieser Erfindung sind Gase, beispielsweise verflüssigtes CO2, und leichtflüchtige Flüssigkeiten, beispielsweise Kohlenwasserstoffe mit 3 bis 5 Kohlenstoff-Atomen, bevorzugt cyclo-, iso- und n-Pentan, Fluorkohlenwasserstoffe, bevorzugt HFC 245fa, HFC 134a und HFC 365mfc, Fluorchlorkohlenwasserstoffe, bevorzugt HCFC 141b, Sauerstoff-haltige Verbindungen wie Methylformiat und Dimethoxymethan, oder Chlorkohlenwasserstoffe, bevorzugt 1,2-Dichlorethan.If additional blowing agents are present in the composition according to the invention, these may be physical or chemical blowing agents. Preferably, the composition comprises physical blowing agents. Suitable physical blowing agents for the purposes of this invention are gases, for example liquefied CO 2 , and volatile liquids, for example hydrocarbons having 3 to 5 carbon atoms, preferably cyclo, iso and n-pentane, hydrofluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, chlorofluorocarbons, preferably HCFC 141b, oxygen-containing compounds such as methyl formate and dimethoxymethane, or chlorohydrocarbons, preferably 1,2-dichloroethane.
Neben oder an Stelle von Wasser und gegebenenfalls physikalischen Treibmitteln können auch andere chemische Treibmittel eingesetzt werden, die mit Isocyanaten unter Gasentwicklung reagieren, wie beispielsweise Ameisensäure.In addition to or instead of water and optionally physical blowing agents, other chemical blowing agents can be used which react with isocyanates to evolve gas, such as formic acid.
Als Flammschutzmittel kann die erfindungsgemäße Zusammensetzung alle bekannten und zur Herstellung von Polyurethan- oder Polyisocyanurat-Hartschaumstoffen geeigneten Flammschutzmittel aufweisen. Geeignete Flammschutzmittel im Sinne dieser Erfindung sind bevorzugt flüssige organische Phosphor-Verbindungen, wie halogenfreie organische Phosphate, z.B. Triethylphosphat (TEP), halogenierte Phosphate, z.B. Tris(1-chlor-2-propyl)phosphat (TCPP) und Tris(2-chlorethyl)phosphat (TCEP) und organische Phosphonate, z.B. Dimethylmethanphosphonat (DMMP), Dimethylpropanphosphonat (DMPP), oder Feststoffe wie Ammoniumpolyphosphat (APP) und roter Phosphor. Des Weiteren sind als Flammschutzmittel halogenierte Verbindungen, beispielsweise halogenierte Polyole, sowie Feststoffe, wie Blähgraphit und Melamin, geeignet.As flame retardants, the composition according to the invention may comprise all known flame retardants which are suitable for the production of rigid polyurethane or polyisocyanurate foams. Suitable flame retardants in the context of this invention are preferably liquid organic phosphorus compounds, such as halogen-free organic phosphates, eg triethyl phosphate (TEP), halogenated phosphates, eg tris (1-chloro-2-propyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP) and organic Phosphonates, for example dimethylmethanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), or solids such as ammonium polyphosphate (APP) and red phosphorus. Furthermore, halogenated compounds, for example halogenated polyols, and solids, such as expandable graphite and melamine, are suitable as flame retardants.
Das erfindungsgemäße Verfahren zur Herstellung von Polyurethan- oder Polyisocyanurat-Hartschaumstoffen, zeichnet sich dadurch aus, dass eine wie oben beschriebene, erfindungsgemäße Zusammensetzung umgesetzt wird. Eine zusammenfassende Darstellung des Stands der Technik, der verwendeten Rohstoffe und anwendbaren Verfahren findet sich in
Mit der erfindungsgemäßen Zusammensetzung bzw. mit dem erfindungsgemäßen Verfahren können Polyurethan- bzw. Polyisocyanurat-Hartschäume hergestellt werden.Polyurethane or polyisocyanurate rigid foams can be produced with the composition according to the invention or with the method according to the invention.
Eine bevorzugte Zusammensetzung, insbesondere eine Polyurethan- bzw. Polyisocyanurat-Hartschaumformulierung im Sinne dieser Erfindung würde Polyurethan- bzw. Polyisocyanurat-Hartschäume mit einem Raumgewicht von 5 bis 200 kg/m3, bevorzugt von 5 bis 50 kg/m3 ergeben und hätte die folgende Zusammensetzung:
Da die erfindungsgemäße Zusammensetzung, von wenigen Ausnahmen abgesehen, vor ihrer Umsetzung in zwei Komponenten aufgeteilt ist, müssen zu deren Umsetzung die Komponenten miteinander vermischt werden. Dies kann nach allen dem Fachmann geläufigen Verfahren erfolgen, beispielsweise im Handmischverfahren oder bevorzugt mit Hilfe von Nieder- bzw. Hochdruck-Verschäumungsmaschinen. Dabei können diskontinuierliche Verfahren, beispielsweise zur Produktion von Formschäumen, Kühlschränken und Paneelen, oder kontinuierliche Verfahren, beispielsweise bei Dämmplatten und Metallverbundelementen (im sogenannten Doppelband-Verfahren), bei Blöcken oder bei Sprühverfahren zum Einsatz kommen.Since, apart from a few exceptions, the composition according to the invention is divided into two components before being reacted, the components must be mixed with one another in order to react them. This can be done by all methods familiar to the person skilled in the art, for example by hand mixing or preferably by means of low or high pressure foaming machines. In this context, discontinuous processes, for example for the production of molded foams, refrigerators and panels, or continuous processes, for example in insulation boards and metal composite elements (in the so-called double-belt process), in blocks or in spray processes can be used.
Ein Spezialfall stellen die 1- und 1,5-Komponenten-Dosenschäume dar. Bei dieser Anwendung wird die erfindungsgemäße Zusammensetzung bereits bei Abfüllung in eine Aerosol-Dose zur Reaktion gebracht, wobei sich aus dem Polyol, sowie allen anderen gegenüber Isocyanat reaktiven Komponenten, und dem im Überschuss vorliegenden Isocyanat ein Präpolymer bildet. Beim Gebrauch wird dieses Präpolymer mit Hilfe eines Treibgases als Schaum aus der Aerosol-Dose ausgetragen und härtet durch Nachvernetzung unter dem Einfluss von (Luft-)Feuchtigkeit aus. Auch in dieser Anwendung können die erfindungsgemäßen Polyethersiloxane als Schaumstabilisatoren eingesetzt werden.A special case is the 1- and 1.5-component can foams. In this application, the composition according to the invention is already reacted when filled into an aerosol can, which consists of the polyol, as well as all other isocyanate-reactive components, and the excess isocyanate forms a prepolymer. In use, this prepolymer is discharged from the aerosol can as a foam with the aid of a propellant gas and cures by post-crosslinking under the influence of (air) moisture. Also in this Application, the polyether siloxanes according to the invention can be used as foam stabilizers.
Durch das erfindungsgemäße Verfahren sind die erfindungsgemäßen Polyurethan- oder Polyisocyanurat-Hartschaumstoffe erhältlich. Vorzugsweise enthalten die erfindungsgemäßen Polyurethan- oder Polyisocyanurat-Hartschaumstoffe 0,1 bis 10 Massenteile, bevorzugt 0,5 bis 5 Massenteile und besonders bevorzugt von 1 bis 3 Massenteile bezogen auf 100 Massenteile Polyolkomponente der erfindungsgemäßen Polyethersiloxane in gebundener und/oder ungebundener Form.By the process according to the invention, the polyurethane or polyisocyanurate rigid foams according to the invention are obtainable. The rigid polyurethane or polyisocyanurate foams according to the invention preferably contain 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass and more preferably 1 to 3 parts by mass, based on 100 parts by mass of polyol component of the polyethersiloxanes according to the invention in bound and / or unbound form.
Die erfindungsgemäßen Polyurethan- oder Polyisocyanurat-Hartschaumstoffe können als oder zur Herstellung von Dämmplatten und Isolationsmittel bzw. Isoliermaterialien verwendet werden. Auf diese Weise sind Kühlapparaturen, wie z. B. Kühl- oder Gefrierschränke, zugänglich, die sich dadurch auszeichnen, dass sie als Isoliermaterial einen erfindungsgemäßen Polyurethan- oder Polyisocyanurat-Hartschaumstoff aufweisen.The rigid polyurethane or polyisocyanurate foams according to the invention can be used as or for the production of insulating boards and insulating or insulating materials. In this way, cooling equipment, such. As refrigerators or freezers, accessible, which are characterized in that they have as insulating a polyurethane or polyisocyanurate rigid foam according to the invention.
Nachfolgend werden einige besonders bevorzugte Anwendungen beschrieben, ohne dass der Gegenstand der Erfindung auf diese beschränkt sein soll.Hereinafter, some particularly preferred applications will be described without the scope of the invention being limited thereto.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung werden die erfindungsgemäßen Zusammensetzungen als PUR Formulierungen (Index kleiner 200) eingesetzt, die bei der Verschäumung in einem diskontinuierlichen Prozess in einer Form verwendet werden. Oftmals sind diese Formen so dimensioniert, dass die schäumende Mischung lange Fließwege hat und dadurch die Anfälligkeit für Schaumstörungen steigt. Hier kann bei der Verwendung der erfindungsgemäßen Zusammensetzungen die Anfälligkeit für Schaumstörungen minimiert werden.In a preferred embodiment of the present invention, the compositions of the invention are used as PUR formulations (index less than 200), which are used in the foaming in a batch process in a mold. Often, these shapes are dimensioned so that the foaming mixture has long flow paths, thereby increasing the susceptibility to foam disturbances. Here, when using the compositions of the invention susceptibility to foam disorders can be minimized.
Bevorzugt werden die erfindungsgemäßen Zusammensetzungen bei der Herstellung von Kühlschränken oder anderen Kühlaggregaten eingesetzt. Hierbei wird in einem diskontinuierlichen Prozess die schäumende Mischung in die Wandung des sogenannten Kabinetts (und separat der Tür) injiziert und muss dort den zur Verfügung stehenden Raum zwischen der äußeren Deckschicht und der inneren Deckschicht (Inliner) ausfüllen. Hierbei ist der Schaum einem Fließstress unterzogen, was die Gefahr der Fehlerbildung erhöht. Zusätzlich spielen die verwendeten Materialien eine wichtige Rolle. Der Inliner besteht meist aus Kunststoff und die Außenhülle des Kühlschranks aus einer Metalldeckschicht. Hier darf es zu keinen Schaumfehlern kommen, die aus der Wechselwirkung mit diesen Materialien oder eventuell darauf befindlichen Verschmutzungen herrühren. Die erfindungsgemäßen Zusammensetzungen zeigen hier eine überlegene Fähigkeit Schaumfehler unter diesen Bedingungen zu unterdrücken. Dadurch erhält man auch bei der Verwendung von dünnen Deckschichten, wie z. B. Metalldeckschichten und/oder Kunststoffdeckschichten, eine glatte Oberfläche des Kühlschranks, da die Neigung zur Fehlerbildung an der Grenzschicht unterdrückt ist. Die Kunststoffdeckschichten können z. B. Polypropylen, Polyethylen oder (High Impact Polystyrene) HIPS-Deckschichten sein.The compositions according to the invention are preferably used in the production of refrigerators or other refrigeration units. Here, in a discontinuous process, the foaming mixture is injected into the wall of the so-called cabinet (and separately the door) and there must fill the available space between the outer cover layer and the inner cover layer (inliner). Here, the foam is subjected to flow stress, which increases the risk of error formation. In addition, the materials used play an important role. The inliner is usually made of plastic and the outer shell of the refrigerator made of a metal top layer. There must be no foam defects resulting from the interaction with these materials or any contamination thereon. The compositions of the present invention show a superior ability to suppress foaming defects under these conditions. This gives even with the use of thin cover layers, such. As metal topcoats and / or plastic topcoats, a smooth surface of the refrigerator, since the tendency to form defects on the boundary layer is suppressed. The plastic cover layers can, for. As polypropylene, polyethylene or (high impact polystyrene) HIPS cover layers.
In einer weiteren bevorzugten Ausführungform der vorliegenden Erfindung werden die erfindungsgemäßen Zusammensetzungen bei der Herstellung von Verbundelementen eingesetzt. Hierbei wird in einem diskontinuierlichen Prozess die zu schäumende Zusammensetzung (PUR- und PIR-Rezepturen finden Verwendung) zwischen zwei Deckschichten injiziert. Als Deckschichten kommen verschiedene Materialien in Frage. Meist sind es Metalldeckschichten zur Herstellung von Metallverbundelementen, die dann in der Bauindustrie Verwendung finden. Es können aber auch auf einer oder beiden Seiten Kunststoffdeckschichten eingesetzt werden. Die so erhaltenen Verbundelemente, oft auch Paneele genannt, können Verwendung in diversen Bereichen wie der Bauindustrie (Fassaden), im Automobilbereich (Caravanbereich), dem Messebau (Leichtbauwände) oder der Möbelherstellung finden. Besonders bei der beidseitigen Verwendung von Kunststoffdeckschichten können hierbei sehr leichte Verbundelemente hergestellt werden. Als Deckschichten können beispielsweise folgende Materialien eingesetzt werden: PMMA (Polymethylmethacrylat), HIPS (High Impact Polystyrene), PP (Polypropylen), Resopal, faserverstärkte Papier-Typen. Besondere Probleme können hier von Beschichtungen auf den Metalldeckschichten oder Prozesshilfsmitteln (Trennmittel) auf Kunststoffoberflächen ausgehen, die für die Ausbildung des Schaums nachteilig sein können. Generell zeigen hier die erfindungsgemäßen Zusammensetzungen Vorteile bei den Oberflächenqualitäten, da weniger Schaumfehler auftreten als bei Verwendung von Siloxanen nach dem bisherigen Stand der Technik. Zusätzlich zu den ästhetischen Aspekten kann auch die Haftung der Deckschichten auf dem Schaum verbessert werden.In a further preferred embodiment of the present invention, the compositions according to the invention are used in the production of composite elements. Here, in a discontinuous process, the composition to be foamed (PUR and PIR formulations are used) is injected between two cover layers. Suitable cover layers are various materials. Mostly it is metal cover layers for the production of metal composite elements, which are then in the Construction industry find use. But it can also be used on one or both sides of plastic topcoats. The resulting composite elements, often called panels, can be used in various areas such as the construction industry (facades), in the automotive sector (caravan area), the fair construction (lightweight walls) or furniture manufacturing. Particularly in the case of two-sided use of plastic cover layers, very lightweight composite elements can be produced in this case. For example, the following materials can be used as cover layers: PMMA (polymethyl methacrylate), HIPS (high impact polystyrene), PP (polypropylene), formica, fiber-reinforced paper types. Particular problems here can arise from coatings on the metal cover layers or process aids (release agents) on plastic surfaces, which may be disadvantageous for the formation of the foam. In general, the compositions according to the invention show advantages in terms of surface qualities, since there are fewer foam defects than when using siloxanes according to the prior art. In addition to the aesthetic aspects, the adhesion of the cover layers to the foam can also be improved.
In einer weiteren bevorzugten Ausführungsform werden die erfindungsgemäßen Zusammensetzungen (bzw. die erfindungsgemäße Polyethersiloxane) bei der kontinuierlichen Herstellung von Polyurethan oder Polyisocyanurat basierenden Metall-Paneelen verwendet. Hierbei wird in einem Doppelbandlaminator bei Bandgeschwindikeiten von maximal 25 m/min über einen traversierenden Mischkopf die schäumende Mischung auf die untere Metallschicht aufgetragen. Oftmals sind die Metalldeckschichten hierbei profiliert. Im Laminator erreicht dann die aufsteigende Mischung die obere Deckschicht wodurch ein kontinuierlich gebildetes Metallpaneel entsteht, welches am Austrittsende des Laminators in die gewünschte Länge geschnitten wird. Hierbei muss die schäumende Mischung die oftmals profilierten Deckschichten komplett bedecken und den Raum zwischen den Deckschichten komplett ausfüllen. In den meisten Fällen wird hier die schäumende Mischung aus einem Mischkopf dosiert an dem sich eine sogenannte Giessharfe befinden kann. Mit einer Giessharfe wird die Mischung aus mehreren Öffnungen entlang der Bandrichtung ausgetragen. Um eine gleichmäßige Schaumverteilung über die Breite des Paneels zu erhalten, wird der Mischkopf traversierend über die Breite des Panels bewegt. Eine weitere Aufgabenstellung besteht hier in der Vermeidung von Oberflächendefekten, die hier von Beschichtungen auf den Metalldeckschichten (Coil Coatings) herrühren können, da diese oftmals Entschäumer enthalten, die für den Schaum bzw. die Schaumbildung schädlich sein können. Generell zeigen hier die erfindungsgemäßen Zusammensetzungen Vorteile bei den Oberflächenqualitäten, da weniger Schaumfehler auftreten als bei Verwendung von Polyethersiloxanen nach dem bisherigen Stand der Technik.In a further preferred embodiment, the compositions according to the invention (or the polyether siloxanes according to the invention) are used in the continuous preparation of polyurethane or polyisocyanurate-based metal panels. Here, the foaming mixture is applied to the lower metal layer in a Doppelbandlaminator at Bandgeschwindikeiten a maximum of 25 m / min via a traversing mixing head. Often the metal cover layers are profiled here. In the laminator, the rising mixture then reaches the top surface layer resulting in a continuously formed layer Metal panel is formed, which is cut at the exit end of the laminator to the desired length. Here, the foaming mixture must cover the often profiled cover layers completely and fill the space between the cover layers completely. In most cases, the foaming mixture of a mixing head is dosed here at which a so-called Giessharfe can be. With a Giessharfe the mixture of several openings along the tape direction is discharged. In order to obtain a uniform foam distribution across the width of the panel, the mixing head is traversingly moved across the width of the panel. A further task here consists of avoiding surface defects, which here can result from coatings on the metal coating layers (coil coatings), since these often contain defoamers, which can be detrimental to the foam or foaming. In general, the compositions according to the invention show advantages in terms of surface qualities, since there are fewer foam defects than when using polyethersiloxanes according to the prior art.
In einer weiteren bevorzugten Ausführungsform werden die erfindungsgemäßen Zusammensetzungen (Siloxane) bei der kontinuierlichen Herstellung von Polyurethan oder Polyisocyanurat basierenden Paneelen mit flexiblen Deckschichten verwendet. Hierbei wird in einem Doppelbandlaminator bei Bandgeschwindigkeiten von bis über 50 m/min über einen oder mehrere Mischköpfe die schäumende Mischung auf die untere Deckschicht aufgetragen. Im Laminator erreicht dann die aufsteigende Mischung die obere Deckschicht wodurch ein kontinuierlich gebildetes Paneel entsteht, welches am Austrittsende des Laminatores in die gewünschte Länge geschnitten wird.In a further preferred embodiment, the compositions according to the invention (siloxanes) are used in the continuous production of polyurethane or polyisocyanurate-based panels with flexible cover layers. Here, the foaming mixture is applied to the lower cover layer in a Doppelbandlaminator at belt speeds of up to about 50 m / min via one or more mixing heads. In the laminator, the rising mixture then reaches the upper cover layer, resulting in a continuously formed panel which is cut to the desired length at the exit end of the laminator.
Es können hierbei ein Vielzahl an verschiedenen Deckschichten eingesetzt werden, wie beispielsweise Papier, Aluminium, Bitumen, Faserfließe, Mehrschichtfolien aus diversen Materialien, etc.It can be used here a variety of different cover layers, such as paper, aluminum, bitumen, fiber flow, multilayer films of various materials, etc.
Hierbei muss die schäumende Mischung aufgrund der höheren Bandgeschwindigkeiten in kurzer Zeit möglichst gleichmäßig verfließen, damit ein homogener Schaum ohne Verdichtungen und unregelmäßige Zellgrößenverteilung entstehen kann. Aufgrund der hohen Austragsmengen, die hier benötigt werden, können hierbei auch Anlagen verwendet werden mit mehr als einem Mischkopf, wobei dann die schäumende Mischung in mehreren Strängen auf den Laminator ausgetragen wird. Dieser Prozess wird auch als "finger lay down" bezeichnet.In this case, the foaming mixture must flow as evenly as possible in a short time due to the higher belt speeds, so that a homogeneous foam without compaction and irregular cell size distribution can occur. Due to the high discharge rates, which are needed here, plants can be used here with more than one mixing head, in which case the foaming mixture is discharged in several strands on the laminator. This process is also known as "finger lay down".
Die sehr unterschiedlichen Materialseigenschaften der Deckschichten stellen eine zusätzliche Herausforderung dar, da hier je nach Material Probleme auftreten können, wie beispielsweise Entschäumungseffekte durch Kontaminationen auf den Deckschichten, schlechte Haftung, erhöhter Fließstress bei sehr rauen Oberflächen. Hier steht die Vermeidung von Oberflächendefekten im Vordergrund. Generell zeigen hier die erfindungsgemäßen Zusammensetzungen Vorteile bei den Oberflächenqualitäten, da weniger Schaumfehler auftreten als bei Verwendung von Polyethersiloxanen nach dem bisherigen Stand der Technik.The very different material properties of the cover layers represent an additional challenge since, depending on the material, problems can occur here, such as defoaming effects due to contaminations on the cover layers, poor adhesion, increased flow stress on very rough surfaces. Here, the prevention of surface defects is in the foreground. In general, the compositions according to the invention show advantages in terms of surface qualities, since there are fewer foam defects than when using polyethersiloxanes according to the prior art.
Die vorliegende Erfindung wird an Hand der Figuren näher erläutert ohne darauf beschränkt zu sein.
In den nachfolgend aufgeführten Beispielen wird die vorliegende Erfindung beispielhaft beschrieben, ohne dass die Erfindung, deren Anwendungsbreite sich aus der gesamten Beschreibung und den Ansprüchen ergibt, auf die in den Beispielen genannten Ausführungsformen beschränkt sein soll.In the examples given below, the present invention is described by way of example, without the invention, the scope of application of which is apparent from the entire description and the claims, to be limited to the embodiments mentioned in the examples.
Es wurden die in Tabelle 2 angegebenen Polyethersiloxane hergestellt. Die Angaben in Tabelle 2 basieren auf Formel (I). Die Strukturbeschreibung der Polyether-Reste R gibt die Sequenz der enthaltenen Alkylenoxid-Bausteine entsprechend der über eine sequenzielle Dosierung der Alkylenoxide bei der Herstellung der Polyether gesteuerten Block-Abfolge an.
In den folgenden Beispielen 1a bis 1c wird exemplarisch die Herstellung des Polyethersiloxans PES I beschrieben. Alle anderen Polyethersiloxane aus Tabelle 2 wurden durch Umsetzung in analogen Verfahren erhalten.In the following Examples 1a to 1c, the preparation of the polyethersiloxane PES I is described by way of example. All other polyethersiloxanes from Table 2 were obtained by reaction in analogous methods.
Ein Gemisch aus 244.7 g Decamethylcyclopentasiloxan (D5), 31.7 g Poly(methyl)wasserstoffsiloxan PTF1 (SiH-Gehalt 15.75 Val/kg) und 14.5 g Hexamethyldisiloxan (HMDS) wurde analog zu Beispiel 1 aus
Die Herstellung des Allyl-Polyethers erfolgte analog zu der in Beispiel 1 der Schrift
Die Hydrosilylierungsreaktion (Umsetzungen des Si-H-funktionellen Siloxans mit den Allylpolyethern) wurde entsprechend dem Beispiel 1 in der Schrift
Die anwendungstechnischen Vorteile gegenüber dem Stand der Technik, die der Einsatz der erfindungsgemäßen Polyethersiloxane in Hartschaum-Formulierungen ermöglicht, werden im Folgenden anhand von Anwendungsbeispielen aufgezeigt.The performance advantages over the prior art, which allows the use of the polyether siloxanes according to the invention in rigid foam formulations are shown below with reference to application examples.
Die Durchführung der Vergleichsverschäumungen erfolgte im Handmischverfahren. Dazu wurden Polyol, Flammschutzmittel, Katalysatoren, Wasser, konventioneller bzw. erfindungsgemäßer Schaumstabilisator und Treibmittel in einen Becher eingewogen und mit einem Tellerrührer (6 cm Durchmesser) 30 s bei 1000 Upm vermischt. Durch erneutes Abwiegen wurde die beim Mischvorgang verdunstete Treibmittelmenge bestimmt und wieder ergänzt. Jetzt wurde das MDI zugegeben, die Reaktionsmischung mit dem beschriebenen Rührer 5 s bei 3000 Upm verrührt und sofort in eine thermostatisierte Aluminiumform überführt, welche mit Polyethylenfolie ausgekleidet war. Formtemperatur und Geometrie variierten dabei je nach Schaumformulierung. Die Einsatzmenge an Schaumformulierung war dabei so bemessen, dass sie um 15 % über der zur Mindestbefüllung der Form notwendigen Menge lag.The comparative foams were carried out by hand mixing. These were polyol, flame retardants, catalysts, water, conventional or inventive foam stabilizer and blowing agents in Weighed a beaker and mixed with a paddle stirrer (6 cm diameter) for 30 s at 1000 rpm. By reweighing, the amount of blowing agent evaporated during the mixing process was determined and supplemented again. Now, the MDI was added, the reaction mixture stirred with the described stirrer at 3000 rpm for 5 seconds and immediately transferred to a thermostated aluminum mold lined with polyethylene film. Mold temperature and geometry varied depending on the foam formulation. The amount of foam formulation used was such that it was 15% above the amount required for the minimum filling of the mold.
Einen Tag nach der Verschäumung wurden die Schaumstoffe analysiert. Oberfläche und Innenstörungen wurden subjektiv anhand einer Skala von 1 bis 10 beurteilt, wobei 10 einen ungestörten Schaum und 1 einen extrem stark gestörten Schaum repräsentiert. Die Porenstruktur (mittlere Zahl der Zellen pro 1 cm) wurde auf einer Schnittfläche optisch durch Vergleich mit Vergleichsschäumen beurteilt. Die Wärmeleitzahl wurde an 2,5 cm dicken Scheiben mit einem Gerät vom Typ Hesto Lambda Control bei Temperaturen an Probenunter- und -oberseite von 10 °C und 36 °C gemessen. Der prozentuale Volumenanteil an geschlossenen Zellen wurde mit einem Gerät vom Typ AccuPyc 1330 der Firma Micromeritics bestimmt. Die Stauchhärten der Schaumstoffe wurden an würfelförmigen Probekörpern mit 5 cm Kantenlänge nach DIN 53421 bis zu einer Stauchung von 10 % gemessen (angegeben ist die in diesem Messbereich maximal aufgetretene Druckspannung).One day after foaming, the foams were analyzed. Surface and internal disturbances were assessed subjectively on a scale of 1 to 10, with 10 representing undisturbed foam and 1 extremely disturbed foam. The pore structure (average number of cells per 1 cm) was assessed optically on a cut surface by comparison with comparative foams. The thermal conductivity was measured on 2.5 cm thick disks with a Hesto Lambda Control instrument at temperatures of 10 ° C and 36 ° C at the top and bottom of the sample. The percentage by volume of closed cells was determined using an instrument of the AccuPyc 1330 type from Micromeritics. The compression hardnesses of the foams were measured on cube-shaped test specimens with 5 cm edge length according to DIN 53421 up to a compression of 10% (stated is the maximum compressive stress which has occurred in this measuring range).
Es wurde eine für dieses Einsatzgebiet abgestimmte Formulierung verwendet (siehe Tabelle 3), die jeweils mit drei erfindungsgemäßen Polyethersiloxan-Schaumstabilisatoren (PES I, PES II und PES III) und zwei nicht erfindungsgemäßen Polyethersiloxan-Schaumstabilisatoren (Tegostab B 1048, ein ausschließlich Butylverkapptes Polyethersiloxan ohne freie OH-Gruppen, und Tegostab B 8408, ein OH-funktionelles Polyethersiloxan mit über 60% primären OH-Gruppen, beide von der Firma Evonik Goldschmidt GmbH) verschäumt wurde. Dabei wurde die Reaktionsmischung in eine auf 45 °C thermostatisierte Aluminiumform von 145 cm x 14,5 cm x 3,5 cm Größe eingetragen.
** polymeres MDI der Firma Bayer, 200 mPa*s, 31,5 Gew.-% NCO, Funktionalität 2,7
** polymeric MDI from Bayer, 200 mPa * s, 31.5 wt .-% NCO, functionality 2.7
Die in Tabelle 4 dargestellten Ergebnisse zeigen, dass die erfindungsgemäßen Polyethersiloxane durchweg zu Hartschäumen führen, die niedrigere Wärmeleitfähigkeiten aufweisen als solche, bei denen die Polyethersiloxane gemäß dem Stand der Technik eingesetzt wurden.. Bei PES II und PES III ist außerdem die Schaumoberfläche weniger stark gestört als bei den Vergleichsstabilisatoren.
Es wurde eine für dieses Einsatzgebiet abgestimmte Formulierung verwendet (siehe Tabelle 5), die jeweils mit einem erfindungsgemäßen Polyethersiloxan-Schaumstabilisator (PES IV) und zwei nicht erfindungsgemäßen Polyethersiloxan-Schaumstabilisatoren (Tegostab B 8443, ein vollständig endverkapptes Polyethersiloxan ohne freie OH-Gruppen, und Tegostab B 8486, ein OH-funktionelles Polyethersiloxan mit ausschließlich primären OH-Gruppen, beide von der Firma Evonik Goldschmidt GmbH) verschäumt wurde. Dabei wurde die Reaktionsmischung in eine auf 40 °C thermostatisierte Aluminiumform von 50 cm x 50 cm x 5 cm Größe eingetragen, in die zuvor auf den Boden eine Stahlblech-Deckschicht eingelegt wurde. Am Folgetag wurde das Blech vom Schaum abgezogen und der Schaum anschließend beurteilt.
Die in Tabelle 6 dargestellten Ergebnisse zeigen, dass das erfindungsgemäße Polyethersiloxane wiederum niedrigere Wärmeleitfähigkeiten bietet, als die beiden nicht erfindungsgemäßen Vergleichs-Stabilisatoren. Nach dem Abziehen der Stahlblech-Deckschicht von der Schaumunterseite werden die darunterliegenden Schaumdefekte sichtbar.
Das erfindungsgemäße Polyethersiloxan PES IV zeigt eine deutliche Reduktion der Lunkerbildung und bietet folglich eine bessere Oberflächenqualität als die Vergleichsprodukte.
** die Schaumqualität der Unterseite nach abziehen des Blechs zeigen
** show the foam quality of the underside after removing the sheet
Es wurde eine für dieses Einsatzgebiet abgestimmte Formulierung verwendet (siehe Tabelle 7), die jeweils mit einem erfindungsgemäßen Polyethersiloxan-Schaumstabilisator (PES V) und zwei nicht erfindungsgemäßen Polyethersiloxan-Schaumstabilisatoren (Tegostab B 1048, ein ausschließlich Butylverkapptes Polyethersiloxan ohne freie OH-Gruppen und Tegostab B 8466, ein OH-funktionelles Polyethersiloxan mit ausschließlich primären OH-Gruppen, beide von der Firma Evonik Goldschmidt GmbH) verschäumt wurde. Dabei wurde die Reaktionsmischung in eine auf 50 °C thermostatisierte Aluminiumform von 50 cm x 25 cm x 5 cm Größe eingetragen.
** polymeres MDI der Firma Bayer, 200 mPa*s, 31,5 Gew.-% NCO, Funktionalität 2,7
** polymeric MDI from Bayer, 200 mPa * s, 31.5 wt .-% NCO, functionality 2.7
Die in Tabelle 8 dargestellten Ergebnisse zeigen abermals, das s die unter Einsatz des erfindungsgemäßen Polyethersiloxans hergestellten Schäume niedrigere Wärmeleitfähigkeiten und eine bessere Schaumqualität an der Unterseite aufweisen als die unter Verwendung der beiden nicht erfindungsgemäßen Vergleichsprodukte erhaltenen Schäume.
Claims (12)
R1-Si (CH3) 2-O- [-Si (CH3) 2-O-]n- [-Si (CH3) R-O-]m -Si (CH3) 2-R2 (I) mit
R, R1 und R2 gleich oder verschieden,
R gleich oder Verschieden - (CH2) x-O- (CH2-CR'R'' -O)y-R''',
R', R'' gleich oder verschieden -H, -CH3, -CH2CH3, oder Phenyl-Rest,
R ''' = -H, -Alkyl- oder -Acyl-Rest,
R1 und/oder R2 gleich Methyl oder R,
wobei die Alkylenoxid-Bausteine (CH2-CR'R'-O) innerhalb eines Polyether-Restes R gleich oder unterschiedlich sein können und die Polyether-Reste R innerhalb eines Polyethersiloxan-Moleküls der Formel (I) gleich oder unterschiedlich sein können, dadurch gekennzeichnet, dass im Mittel (Zahlenmittel, gemittelt über alle Verbindungen der Formel (I))
n+m+2 = >10 bis 200,
m = 0 bis 40 für R1 und/oder R2 gleich R bzw. m = 1 bis 40 für R1 und R2 gleich -CH3,
x = 2 bis 10,
y = 1 bis 50,
mindestens 25% der Reste R''' gleich Wasserstoff sind und unter allen Polyether-Resten R, die eine Endgruppe R''' = -H besitzen, mindestens 50% eine sekundäre oder tertiäre OH-Endgruppe aufweisen.Polyethersiloxanes of the formula (I)
R 1 -Si (CH 3 ) 2 -O- [-Si (CH 3 ) 2 -O-] n - [-Si (CH 3 ) RO-] m -Si (CH 3 ) 2 -R 2 (I) With
R, R 1 and R 2 are the same or different,
R is the same or different - (CH 2 ) x -O- (CH 2 -CR'R "-O) y -R '",
R ', R "are identical or different and are -H, -CH 3 , -CH 2 CH 3 , or phenyl radical,
R '''= -H, -alkyl or -acyl radical,
R 1 and / or R 2 are methyl or R,
wherein the alkylene oxide units (CH 2 -CR'R'-O) within a polyether radical R may be the same or different and the polyether radicals R within a polyether siloxane molecule of formula (I) may be the same or different, characterized in that an average (number average, averaged over all compounds of the formula (I))
n + m + 2 => 10 to 200,
m = 0 to 40 for R 1 and / or R 2 is R or m = 1 to 40 for R 1 and R 2 is -CH 3 ,
x = 2 to 10,
y = 1 to 50,
at least 25% of the radicals R '"are hydrogen and, of all the polyether radicals R which have an end group R'" = -H, at least 50% have a secondary or tertiary OH end group.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL11189690T PL2465892T3 (en) | 2010-12-16 | 2011-11-18 | Silicon stabilisers for polyurethane or polyisocyanurate rigid foams |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102010063237A DE102010063237A1 (en) | 2010-12-16 | 2010-12-16 | Silicone stabilizers for rigid polyurethane or polyisocyanurate foams |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2465892A1 true EP2465892A1 (en) | 2012-06-20 |
EP2465892B1 EP2465892B1 (en) | 2015-04-29 |
Family
ID=45062967
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20110189690 Active EP2465892B1 (en) | 2010-12-16 | 2011-11-18 | Silicon stabilisers for polyurethane or polyisocyanurate rigid foams |
Country Status (9)
Country | Link |
---|---|
US (1) | US8957121B2 (en) |
EP (1) | EP2465892B1 (en) |
KR (1) | KR101884023B1 (en) |
CN (1) | CN102604107B (en) |
BR (1) | BRPI1105503B1 (en) |
CA (1) | CA2762568C (en) |
DE (1) | DE102010063237A1 (en) |
MX (1) | MX2011013835A (en) |
PL (1) | PL2465892T3 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015101497A1 (en) | 2013-12-30 | 2015-07-09 | Evonik Degussa Gmbh | Composition suitable for preparing polyurethane- or polyisocyanurate rigid foams |
WO2017220332A1 (en) | 2016-06-23 | 2017-12-28 | Evonik Degussa Gmbh | Composition suitable for preparing polyurethane- or polyisocyanurate rigid foams |
EP3677610A1 (en) | 2019-01-07 | 2020-07-08 | Evonik Operations GmbH | Preparation of polyurethane foam |
WO2020144003A1 (en) | 2019-01-07 | 2020-07-16 | Evonik Operations Gmbh | Production of rigid polyurethane foam |
EP3919539A1 (en) | 2020-06-04 | 2021-12-08 | Evonik Operations GmbH | Preparation of polyurethane foam |
EP3957669A1 (en) | 2020-08-20 | 2022-02-23 | Evonik Operations GmbH | Preparation of polyurethane foam |
EP3894454A4 (en) * | 2018-12-14 | 2022-07-27 | Dow Global Technologies LLC | Rigid polyisocyanurate and polyurethane foams and methods for preparing the same |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102010063241A1 (en) * | 2010-12-16 | 2012-06-21 | Evonik Goldschmidt Gmbh | Silicone stabilizers for rigid polyurethane or polyisocyanurate foams |
DE102011109547A1 (en) | 2011-08-03 | 2013-02-07 | Evonik Goldschmidt Gmbh | Polysiloxanpolyether copolymers with carbonate group-containing (polyether) radicals and their use as stabilizer for the production of polyurethane foams |
EP2970571B1 (en) * | 2013-03-15 | 2020-11-25 | Stepan Company | Polyester polyols imparting improved flammability properties |
DE102013226575B4 (en) | 2013-12-19 | 2021-06-24 | Evonik Operations Gmbh | Composition suitable for the production of polyurethane foams, containing at least one unsaturated fluorocarbon or unsaturated fluorocarbon as blowing agent, polyurethane foams, processes for their production and their use |
TW201542682A (en) * | 2014-02-27 | 2015-11-16 | Sekisui Chemical Co Ltd | In-situ foaming system for forming flame-retardant polyurethane foam in situ |
DE102014215382A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
DE102014215388A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
DE102014215384A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
EP3029087A1 (en) | 2014-12-05 | 2016-06-08 | Evonik Degussa GmbH | Method for the preparation of low-viscosity polyether siloxanes |
PL3115389T3 (en) | 2015-07-07 | 2020-09-07 | Evonik Operations Gmbh | Preparation of polyurethane foam |
CN105199108B (en) * | 2015-08-20 | 2018-06-26 | 江苏奥斯佳材料科技有限公司 | A kind of foam stabiliser and preparation method thereof and the application in synthesis of polyurethane expanded material |
WO2018015260A1 (en) | 2016-07-19 | 2018-01-25 | Evonik Degussa Gmbh | Use of polyolesters for producing porous plastic coatings |
CN109942823A (en) * | 2017-12-21 | 2019-06-28 | 江苏美思德化学股份有限公司 | With the polyether silicones copolymer and synthetic method of good emulsifiability and application |
CN112513120A (en) * | 2018-07-31 | 2021-03-16 | 陶氏环球技术有限责任公司 | Compositions containing isocyanate-compatible silicone stabilizers |
MX2021004117A (en) * | 2018-10-09 | 2021-07-16 | Dow Global Technologies Llc | A rigid polyurethane foam formulation and foam made therefrom. |
US20220041828A1 (en) * | 2018-10-09 | 2022-02-10 | Dow Global Technologies Llc | A rigid polyurethane foam formulation and foam made therefrom |
CN112375195B (en) * | 2020-11-13 | 2022-07-08 | 南京红宝丽新材料有限公司 | Composition for reacting with isocyanate, rigid polyurethane plate and preparation method thereof |
WO2022269684A1 (en) * | 2021-06-21 | 2022-12-29 | ダウ・東レ株式会社 | Foam booster, premix solution including same, composition for polyurethane foam molding including these, and polyurethane foam with improved hydrophobicity |
TR2022000370A2 (en) * | 2022-01-12 | 2022-02-21 | Assan Panel Sanayi Ve Ticaret Anonim Sirketi | HARD POLYURETHANE FOAM COMPOSITION SUITABLE FOR USE IN SANDWICH PANEL INDUSTRY APPLICATIONS |
Citations (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4014825A (en) | 1975-12-29 | 1977-03-29 | Union Carbide Corporation | Tertiary alcohol-bearing organosilicone polymers |
US4052495A (en) * | 1975-05-19 | 1977-10-04 | Dow Corning Corporation | Method of obtaining release of polyurethane polymers and compositions therefor |
US4136250A (en) * | 1977-07-20 | 1979-01-23 | Ciba-Geigy Corporation | Polysiloxane hydrogels |
US4147847A (en) | 1973-11-14 | 1979-04-03 | Dow Corning Corporation | Method of preparing flexible flame retardant polyether based one-shot polyurethane foams and compositions therefore |
US4746683A (en) | 1987-09-29 | 1988-05-24 | Union Carbide Corporation | Polyether silicone copolymers with secondary or tertiary hydroxy termination for stabilizing high resiliency urethane foam |
US4797501A (en) * | 1986-12-31 | 1989-01-10 | Union Carbide Corporation | Silicone-based stabilizers useful in the preparation of improved polyurethane foams |
US4855379A (en) | 1988-03-08 | 1989-08-08 | Union Carbide Corporation | Silicone surfactants containing cyclic siloxane pendants |
EP0493836A1 (en) | 1990-12-31 | 1992-07-08 | OSi Specialties, Inc. | Surfactants for manufacture of urethane foams |
US5169872A (en) * | 1992-05-11 | 1992-12-08 | Dow Corning Corporation | Process for preparing rigid polyurethane and polyisocyanurate foams having enhanced benefits |
EP0533202A1 (en) | 1991-09-20 | 1993-03-24 | Union Carbide Chemicals & Plastics Technology Corporation | Use of capped surfactants for production of rigid polyurethane foams blown with hydrochlorofluorocarbons |
EP0293125B1 (en) | 1987-05-19 | 1994-05-18 | Dow Corning Corporation | Surfactant composition for rigid urethane and isocyanurate foams |
JPH0892404A (en) * | 1994-09-27 | 1996-04-09 | Nippon Unicar Co Ltd | Flexible polyurethane foam, its preparation, and foam stabilizer therefor |
US6071977A (en) * | 1996-10-31 | 2000-06-06 | Ck Witco Corporation | Hydrosilation in high boiling natural vegetable oils |
DE19940797A1 (en) | 1999-08-27 | 2001-03-01 | Goldschmidt Ag Th | Obtained by Akoxylierung block copolymers, styrene oxide-containing polyalkylene oxides and their use |
EP0877045B1 (en) | 1997-05-08 | 2002-01-16 | Air Products And Chemicals, Inc. | Silicone surfactants for rigid polyurethane foam made with third generation blowing agents |
EP1360223A2 (en) | 2001-01-08 | 2003-11-12 | Dow Corning Corporation | Certain silicone polyethers, methods for making them and uses |
EP1439200A1 (en) | 2003-01-16 | 2004-07-21 | Goldschmidt AG | Equilibration of siloxanes |
EP1520870A1 (en) | 2003-10-04 | 2005-04-06 | Goldschmidt GmbH | Process for manufacturing organic silicon compounds |
EP1544235A1 (en) | 2003-12-15 | 2005-06-22 | Air Products And Chemicals, Inc. | Silicone surfactants for rigid polyurethane foam made with hydrocarbon blowing agents |
DE102006030531A1 (en) | 2006-07-01 | 2008-01-03 | Goldschmidt Gmbh | Silicone stabilizers for flame-retardant rigid polyurethane or polyisocyanurate foams |
CN101125952A (en) * | 2007-08-08 | 2008-02-20 | 南京德美世创化工有限公司 | Polyurethane foam stabilizer with low density and low thermal conductivity factor and preparation method thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2558523A1 (en) * | 1975-12-24 | 1977-07-07 | Bayer Ag | PROCESS FOR MANUFACTURING NEW POLYSILOXANE-POLYOXYALKYLENE COPOLYMER |
US4163830A (en) * | 1975-12-24 | 1979-08-07 | Bayer Aktiengesellschaft | Process for the production of new polysiloxane-polyoxyalkylene copolymers with reduced burning properties |
DE3812481A1 (en) * | 1987-08-26 | 1989-03-09 | Bayer Ag | WATERPROOF POLYMER PREPARATION |
BR0003942A (en) * | 1999-09-01 | 2001-04-03 | Dow Corning | Polyether silicone copolymers and their use in flexible molded polyurethane foams |
CN1365990A (en) * | 2000-12-22 | 2002-08-28 | 陶氏康宁公司 | Siloxane polyether copolymer for preparing polyurethane flexible molding foamed plastics |
DE102006038661A1 (en) * | 2006-08-18 | 2008-02-21 | Evonik Goldschmidt Gmbh | Use of low-viscosity aqueous polyurethane hot flexible foam stabilizer solutions comprising polyethersiloxanes in the production of hot-cure polyurethane foams |
CN100509128C (en) * | 2007-08-08 | 2009-07-08 | 南京德美世创化工有限公司 | Masked non-ionic surfactant, preparation method and application thereof |
US8044109B2 (en) * | 2008-04-03 | 2011-10-25 | Momentive Performance Materials Inc. | Polyurethane foams containing silicone surfactants |
DE102009003274A1 (en) * | 2009-05-20 | 2010-11-25 | Evonik Goldschmidt Gmbh | Compositions containing polyether-polysiloxane copolymers |
-
2010
- 2010-12-16 DE DE102010063237A patent/DE102010063237A1/en not_active Withdrawn
-
2011
- 2011-11-18 EP EP20110189690 patent/EP2465892B1/en active Active
- 2011-11-18 PL PL11189690T patent/PL2465892T3/en unknown
- 2011-12-13 BR BRPI1105503-0A patent/BRPI1105503B1/en active IP Right Grant
- 2011-12-15 KR KR1020110135435A patent/KR101884023B1/en active IP Right Grant
- 2011-12-15 CA CA2762568A patent/CA2762568C/en active Active
- 2011-12-16 US US13/328,135 patent/US8957121B2/en active Active
- 2011-12-16 CN CN201110431773.1A patent/CN102604107B/en active Active
- 2011-12-16 MX MX2011013835A patent/MX2011013835A/en active IP Right Grant
Patent Citations (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4147847A (en) | 1973-11-14 | 1979-04-03 | Dow Corning Corporation | Method of preparing flexible flame retardant polyether based one-shot polyurethane foams and compositions therefore |
US4052495A (en) * | 1975-05-19 | 1977-10-04 | Dow Corning Corporation | Method of obtaining release of polyurethane polymers and compositions therefor |
US4014825A (en) | 1975-12-29 | 1977-03-29 | Union Carbide Corporation | Tertiary alcohol-bearing organosilicone polymers |
US4136250A (en) * | 1977-07-20 | 1979-01-23 | Ciba-Geigy Corporation | Polysiloxane hydrogels |
US4797501A (en) * | 1986-12-31 | 1989-01-10 | Union Carbide Corporation | Silicone-based stabilizers useful in the preparation of improved polyurethane foams |
EP0293125B1 (en) | 1987-05-19 | 1994-05-18 | Dow Corning Corporation | Surfactant composition for rigid urethane and isocyanurate foams |
US4746683A (en) | 1987-09-29 | 1988-05-24 | Union Carbide Corporation | Polyether silicone copolymers with secondary or tertiary hydroxy termination for stabilizing high resiliency urethane foam |
US4855379A (en) | 1988-03-08 | 1989-08-08 | Union Carbide Corporation | Silicone surfactants containing cyclic siloxane pendants |
EP0493836A1 (en) | 1990-12-31 | 1992-07-08 | OSi Specialties, Inc. | Surfactants for manufacture of urethane foams |
EP0533202A1 (en) | 1991-09-20 | 1993-03-24 | Union Carbide Chemicals & Plastics Technology Corporation | Use of capped surfactants for production of rigid polyurethane foams blown with hydrochlorofluorocarbons |
US5169872A (en) * | 1992-05-11 | 1992-12-08 | Dow Corning Corporation | Process for preparing rigid polyurethane and polyisocyanurate foams having enhanced benefits |
EP0570174B1 (en) | 1992-05-11 | 1996-02-07 | Dow Corning Corporation | Process for preparing rigid polyurethane and polyisocyanurate foams |
JPH0892404A (en) * | 1994-09-27 | 1996-04-09 | Nippon Unicar Co Ltd | Flexible polyurethane foam, its preparation, and foam stabilizer therefor |
US6071977A (en) * | 1996-10-31 | 2000-06-06 | Ck Witco Corporation | Hydrosilation in high boiling natural vegetable oils |
EP0877045B1 (en) | 1997-05-08 | 2002-01-16 | Air Products And Chemicals, Inc. | Silicone surfactants for rigid polyurethane foam made with third generation blowing agents |
DE19940797A1 (en) | 1999-08-27 | 2001-03-01 | Goldschmidt Ag Th | Obtained by Akoxylierung block copolymers, styrene oxide-containing polyalkylene oxides and their use |
EP1360223A2 (en) | 2001-01-08 | 2003-11-12 | Dow Corning Corporation | Certain silicone polyethers, methods for making them and uses |
EP1439200A1 (en) | 2003-01-16 | 2004-07-21 | Goldschmidt AG | Equilibration of siloxanes |
EP1520870A1 (en) | 2003-10-04 | 2005-04-06 | Goldschmidt GmbH | Process for manufacturing organic silicon compounds |
EP1544235A1 (en) | 2003-12-15 | 2005-06-22 | Air Products And Chemicals, Inc. | Silicone surfactants for rigid polyurethane foam made with hydrocarbon blowing agents |
DE102006030531A1 (en) | 2006-07-01 | 2008-01-03 | Goldschmidt Gmbh | Silicone stabilizers for flame-retardant rigid polyurethane or polyisocyanurate foams |
CN101125952A (en) * | 2007-08-08 | 2008-02-20 | 南京德美世创化工有限公司 | Polyurethane foam stabilizer with low density and low thermal conductivity factor and preparation method thereof |
Non-Patent Citations (3)
Title |
---|
"Kunststoffhandbuch", vol. VII, 1983, C. HANSER VERLAG |
"Ullmann's Encyclopedia of Industrial Chemistry", vol. A21, 1992, VCH, pages: 665 - 715 |
HOUBEN-WEYL: "Methoden der organischen Chemie", vol. E20, 1987, THIEME VERLAG, pages: 1561 - 1757 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015101497A1 (en) | 2013-12-30 | 2015-07-09 | Evonik Degussa Gmbh | Composition suitable for preparing polyurethane- or polyisocyanurate rigid foams |
US10351687B2 (en) | 2013-12-30 | 2019-07-16 | Evonik Degussa Gmbh | Composition suitable for production of rigid polyurethane or polyisocyanurate foams |
WO2017220332A1 (en) | 2016-06-23 | 2017-12-28 | Evonik Degussa Gmbh | Composition suitable for preparing polyurethane- or polyisocyanurate rigid foams |
EP3894454A4 (en) * | 2018-12-14 | 2022-07-27 | Dow Global Technologies LLC | Rigid polyisocyanurate and polyurethane foams and methods for preparing the same |
EP3677610A1 (en) | 2019-01-07 | 2020-07-08 | Evonik Operations GmbH | Preparation of polyurethane foam |
WO2020144004A1 (en) | 2019-01-07 | 2020-07-16 | Evonik Operations Gmbh | Production of rigid polyurethane foam |
WO2020144003A1 (en) | 2019-01-07 | 2020-07-16 | Evonik Operations Gmbh | Production of rigid polyurethane foam |
EP3919539A1 (en) | 2020-06-04 | 2021-12-08 | Evonik Operations GmbH | Preparation of polyurethane foam |
EP3957669A1 (en) | 2020-08-20 | 2022-02-23 | Evonik Operations GmbH | Preparation of polyurethane foam |
Also Published As
Publication number | Publication date |
---|---|
BRPI1105503B1 (en) | 2020-03-24 |
CA2762568A1 (en) | 2012-06-16 |
BRPI1105503A2 (en) | 2013-04-09 |
KR101884023B1 (en) | 2018-07-31 |
PL2465892T3 (en) | 2015-09-30 |
CN102604107B (en) | 2015-06-17 |
CN102604107A (en) | 2012-07-25 |
US8957121B2 (en) | 2015-02-17 |
EP2465892B1 (en) | 2015-04-29 |
US20120157558A1 (en) | 2012-06-21 |
MX2011013835A (en) | 2012-06-15 |
CA2762568C (en) | 2018-09-04 |
KR20120067952A (en) | 2012-06-26 |
DE102010063237A1 (en) | 2012-06-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2465892B1 (en) | Silicon stabilisers for polyurethane or polyisocyanurate rigid foams | |
EP2465891B1 (en) | Silicon stabilisers for polyurethane or polyisocyanurate rigid foams | |
EP1873209B1 (en) | Siliconstabilizers for flame retardant polyurethane- resp. polyioscyanurate rigid foams | |
EP2295485B1 (en) | Compound containing lecithin suitable for producing polyurethane foams | |
EP3010951B1 (en) | Isocyanate/siloxane polyether composition | |
EP3090014B1 (en) | Composition suitable for preparing polyurethane or polyisocyanurate rigid foams | |
EP3475351B1 (en) | Composition suitable for preparing polyurethane or polyisocyanurate rigid foams | |
EP2820057B1 (en) | Polyether ester polyols and use of same for producing polyurethane solid foam materials | |
EP3036267B1 (en) | Improved rigid polyurethane and polyisocyanurate foams based on fatty acid modified polyether polyols | |
EP2417181B1 (en) | Polyester polyols from terephthalic acid and oligoalkylenoxides | |
EP3837296A1 (en) | Environmentally friendly driven polyurethane spray foam systems | |
EP2697296B1 (en) | Process for producing rigid polyurethane foams | |
EP2697280A1 (en) | Process for producing rigid polyurethane foams | |
DE102005031975A1 (en) | PUR polyester flexible foams based on polyetheresterpolyols | |
EP2603559B1 (en) | Polyisocyanurate composition | |
EP3677610B1 (en) | Preparation of polyurethane foam | |
EP3498744A1 (en) | Flame retardant rigid polyurethane foams | |
EP3908617A1 (en) | Production of rigid polyurethane foam | |
WO2021260069A1 (en) | Polyisocyanurate resin foam having high compressive strength, low thermal conductivity, and high surface quality | |
EP3957669A1 (en) | Preparation of polyurethane foam | |
EP3919539A1 (en) | Preparation of polyurethane foam |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20111118 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
17Q | First examination report despatched |
Effective date: 20120911 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: EVONIK DEGUSSA GMBH |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20150211 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 724425 Country of ref document: AT Kind code of ref document: T Effective date: 20150515 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502011006709 Country of ref document: DE Effective date: 20150611 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: T3 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: PL Ref legal event code: T3 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150831 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150729 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150730 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150829 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502011006709 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150429 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20160201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151118 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20151118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151130 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151130 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20160729 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151118 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20111118 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 724425 Country of ref document: AT Kind code of ref document: T Effective date: 20161118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150429 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 502011006709 Country of ref document: DE Owner name: EVONIK OPERATIONS GMBH, DE Free format text: FORMER OWNER: EVONIK DEGUSSA GMBH, 45128 ESSEN, DE |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: HC Owner name: EVONIK OPERATIONS GMBH; DE Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGEMENT DE NOM DU PROPRIETAIRE; FORMER OWNER NAME: EVONIK DEGUSSA GMBH Effective date: 20200403 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: HC Owner name: EVONIK OPERATIONS GMBH; DE Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CHANGE OF OWNER(S) NAME Effective date: 20200928 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20221115 Year of fee payment: 12 Ref country code: BE Payment date: 20221118 Year of fee payment: 12 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230526 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20231120 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20231124 Year of fee payment: 13 Ref country code: DE Payment date: 20231121 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20231113 Year of fee payment: 13 Ref country code: BE Payment date: 20231120 Year of fee payment: 13 |